Photocurable resin composition, adhesives, sealants, coatings, cured products containing the same, semiconductor devices, electronic components, and curing, bonding, sealing, and coating methods using the photocurable resin composition.

Abstract

The present invention provides a photocurable resin composition that can be cured by light irradiation alone, an adhesive, a encapsulant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product thereof, and a curing method, bonding method, encapsulation method and coating method using the photocurable resin composition. [Solution] (A) Polymerizable compound, and (B) Exhausted Luminescence (OSL) Materials A photocurable resin composition comprising the following features (a) and (b), satisfying at least one of the following characteristics: (a)(A) The polymerizable compound includes a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. The present invention provides a photocurable resin composition, an adhesive, a encapsulant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product thereof, and a curing method, bonding method, encapsulation method and coating method using the photocurable resin composition.

Description

Technical Field

[0001] The present invention relates to a photocurable resin composition, an adhesive, a sealing material or a coating agent containing the same, a cured product thereof, a semiconductor device or an electronic component containing the cured product, and a curing method, an adhesion method, a sealing method and a coating method using the photocurable resin composition. The present invention also relates to a main agent composition and a photocurable resin composition kit. The present invention further relates to an optically stimulated luminescence (OSL) material.

Background Art

[0002] Adhesives of the type that are temporarily fixed by ultraviolet (UV) irradiation and then fully cured by heat are used in many fields (for example, Patent Documents 1 and 2). When the adhesive contains a filler or the like, the filler or the like becomes a shield for the UV irradiation light, or when the location where the adhesive is applied has a complex shape, the UV irradiation light may be shielded, and there may be a portion in the adhesive where the UV irradiation light does not reach. Therefore, in applications where there are portions that do not receive UV irradiation light and remain uncured, this type of adhesive is used for the purpose of full curing by heat.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the other hand, from the viewpoint of improving productivity and considering the case of applying to members that are vulnerable to heat, an adhesive that can be cured only by light irradiation is desired.

[0005] Therefore, an object of the present invention is to provide a photocurable resin composition that can be cured only by light irradiation, an adhesive or a sealing material containing the same, a cured product thereof, a semiconductor device or an electronic component containing the cured product, and a curing method, an adhesion method, and a sealing method using the photocurable resin composition. **Means for Solving the Problems**

[0006] Specific means for solving the above problems are as follows. The present invention includes a photocurable resin composition in the following aspects, a method for producing the same, an adhesive, a sealing material or a coating agent, a cured product, a semiconductor device or an electronic component, a method for producing the cured product, a method for curing the photocurable resin composition, use of the photocurable resin composition, an adhesion method, a sealing method and a coating method, a main agent composition, a photocurable resin composition kit, and an optically stimulated luminescence (OSL) material. [1] A photocurable resin composition comprising (A) a polymerizable compound and (B) an optically stimulated luminescence (OSL) material satisfying at least one of the following characteristics (a) and (b): (a) The (A) polymerizable compound contains a maleimide compound; (b) The photocurable resin composition contains (C) a photoinitiator, photocurable resin composition. [2] The photocurable resin composition according to [1] above, wherein the (A) polymerizable compound is a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, or any combination thereof. [3] The photocurable resin composition according to [1] or [2] above, for use in curing by irradiation with light having a wavelength of 500 nm or more. [4] The photocurable resin composition according to any one of [1] to [3] above, used as an adhesive, a sealing material or a coating agent for a semiconductor device or an electronic component. [5] A method for producing the photocurable resin composition according to any one of [1] to [4] above, including a step of accumulating excitation energy in the (B) optically stimulated luminescence (OSL) material, a method for producing a photocurable resin composition. [6] An adhesive, sealant, or coating agent comprising the photocurable resin composition described in any one of the above items [1] to [4]. [7] A cured product obtained by curing a photocurable resin composition according to any one of items [1] to [4] above, or an adhesive, sealant, or coating agent according to item [6] above. [8] A semiconductor device or electronic component comprising the cured product described in [7] above. [9] A method for producing a cured product, comprising irradiating a photocurable resin composition according to any one of items [1] to [4] above, or an adhesive, encapsulant, or coating agent according to item [6] above, with light having a wavelength of 500 nm or more.

[10] A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition described in any one of the above items [1] to [4] with light having a wavelength of 500 nm or more.

[11] Use of the photocurable resin composition described in any one of the above items [1] to [4] for curing by irradiation with light of a wavelength of 500 nm or more.

[12] A method for bonding at least two parts with a photocurable resin composition, A step of applying the photocurable resin composition described in any one of the above [1] to [4] to at least one of the at least two parts, and The process includes irradiating at least one of the at least two components, the photocurable resin composition, or both thereof with light having a wavelength of 500 nm or more. Adhesion method.

[13] A method for sealing gaps between or within parts with a photocurable resin composition, A step of applying or injecting the photocurable resin composition described in any one of items [1] to [4] into the gaps between or within the parts, and The photocurable resin composition is irradiated with light of a wavelength of 500 nm or more. Sealing method.

[14] A method for coating the surface of an object with a photocurable resin composition, A step of applying the photocurable resin composition described in any one of items [1] to [4] above to the object, and The process of irradiating the photocurable resin composition with light of a wavelength of 500 nm or more. A coating method including

[15] (A 0 ) Polymerizable compounds, and (B) Exhausted Luminescence (OSL) Materials (C 0 A main component composition that is substantially free of initiators.

[16] (1) The main component composition described in

[15] above, and (2)(C 0 ) Initiator composition containing an initiator A kit of photocurable resin compositions, including [the specified element].

[17] The (2) initiator composition is (A 0 ) A photocurable resin composition kit according to

[16] , further comprising a polymerizable compound.

[18] (A) Exhaustible luminescence (OSL) materials used to cure polymerizable compounds.

[19] The exhausted luminescence (OSL) material according to

[18] , which exhibits exhausted luminescence of wavelength less than 500 nm when irradiated with light of wavelength 500 nm or longer.

[20] The exhausted luminescence (OSL) material according to

[18] or

[19] , wherein the exhausted luminescence (OSL) material is an inorganic ceramic containing impurity elements that form luminescence centers and / or electron trapping centers, and the inorganic ceramic is an oxide or halide containing at least one metallic element selected from the group consisting of alkali metals, alkaline earth metals, earth metals, and rare earth metals.

[21] The impurity element forming the light-emitting center is at least one selected from the group consisting of cerium (Ce), praseodymium (Pr), europium (Eu), thulium (Tm), bismuth (Bi), and carbon (C), and the impurity element forming the electron-trapping center is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni) The exhausted luminescence (OSL) material according to

[20] , which is at least one selected from the group consisting of copper (Cu), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and carbon (C). [Effects of the Invention]

[0007] According to several aspects of the present invention, a photocurable resin composition that can be cured by light irradiation alone, a method for producing the same, an adhesive, a encapsulant or coating agent containing the same, a cured product thereof, a semiconductor device or electronic component containing the cured product thereof, and a curing method, bonding method, encapsulation method and coating method using the photocurable resin composition are provided. Furthermore, according to another aspect of the present invention, a main component composition and a photocurable resin composition kit suitable for producing a photocurable resin composition that can be cured by light irradiation alone are provided.In addition, according to yet another aspect of the present invention, an exhausted luminescence (OSL) material capable of generating short-wavelength OSL suitable for curing polymerizable compounds is provided. [Modes for carrying out the invention]

[0008] In this specification, "(near) ultraviolet light" refers to near-ultraviolet light with a wavelength of 200 nm to 380 nm, "visible light" refers to light with a wavelength of 380 nm to 780 nm, "near-infrared light" refers to light with a wavelength of 780 nm to 2500 nm, and "mid-infrared light" refers to light with a wavelength of 2.5 μm to 25 μm. In this specification, unless otherwise specified, "ultraviolet light" refers to near-ultraviolet light with a wavelength of 200 nm to 380 nm. In this specification, following convention in the field of synthetic resins, the term "resin," which usually refers to a polymer (especially a synthetic polymer), may be used to describe components constituting a curable resin composition before curing, even if the component is not a polymer, for example, a prepolymer compound before curing. In this specification, "(meth)acryloyl group" includes both a methacryloyl group and an acryloyl group. Furthermore, "(meth)acrylate compound" includes both an acrylate compound and a methacrylate compound. Furthermore, in this specification, "photocurable resin composition" may be simply referred to as "resin composition." In this specification, maleimide compounds and (C) photopolymerization initiators are collectively referred to as "initiators" or "(C 0 It is sometimes called an "initiator."

[0009] [Photocurable resin composition] A photocurable resin composition according to one aspect of the present invention is: (A) Polymerizable compounds, and (B) Exhausted Luminescence (OSL) Materials A photocurable resin composition comprising the following features (a) and (b), satisfying at least one of the following characteristics: (a)(A) The polymerizable compound includes a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. This is a photocurable resin composition. According to this embodiment, a photocurable resin composition that can be cured by light irradiation alone can be provided.

[0010] The inventors focused on optically stimulated luminescence (OSL) materials that produce optically stimulated luminescence (OSL). When an optically stimulated luminescence (OSL) material is irradiated with stimulating light of a specific wavelength while it has accumulated excitation energy, it generates the accumulated energy as optically stimulated luminescence (OSL). The inventors found that by incorporating this optically stimulated luminescence (OSL) material together with an initiator into a resin composition and irradiating the resin composition with long-wavelength stimulating light, the optically stimulated luminescence (OSL) material generates short-wavelength OSL within the resin composition, activating the initiator and causing the resin composition to harden. The inventors also confirmed that the hardening of the resin composition proceeds due to optically stimulated luminescence even in the presence of an obstruction to UV irradiation light.

[0011] (A) Polymerizable compound The photocurable resin composition of this embodiment includes (A) a polymerizable compound (hereinafter also referred to as "component (A)"). The polymerizable compound (A) imparts curability and adhesion to the resin composition. In this embodiment, if the photocurable resin composition satisfies feature (a), the polymerizable compound (A) includes a maleimide compound. In this embodiment, if the photocurable resin composition satisfies feature (b), the polymerizable compound (A) can be appropriately selected from radical polymerizable compounds, cationic polymerizable compounds, anionic polymerizable compounds, or any combination thereof, depending on the type of photopolymerization initiator (C) described later.

[0012] Examples of radical polymerizable compounds include, but are not limited to, compounds having unsaturated double bonds such as maleimide compounds, (meth)acrylate compounds, (meth)acrylamide compounds, cyanoacrylate compounds, vinyl ether compounds, styrene compounds, methylene malonates (2-methylene-1,3-dicarbonyl compounds and their derivatives), or mixtures of compounds having unsaturated double bonds and thiol compounds (mixtures capable of ene-thiol reactions).

[0013] Maleimide compounds include monofunctional maleimide compounds having one maleimide group and polyfunctional maleimide compounds having two or more maleimide groups. Maleimide compounds having two maleimide groups are sometimes called bismaleimide compounds. With respect to characteristic (a) described below, maleimide compounds are activated by light with a wavelength of less than 500 nm generated by the (B) exhausted light emission (OSL) material described below, generating radicals and promoting the polymerization of radical polymerizable compounds, including the maleimide compound itself. Since the maleimide compound itself absorbs the light emitted by the (B) exhausted light emission (OSL) material and generates radicals, the photocurable resin composition of this embodiment that satisfies characteristic (a) does not require the use of a photopolymerization initiator, or may require only a small amount. From the viewpoint of workability under fluorescent lighting, maleimide compounds with an absorption wavelength of less than 500 nm are preferred, maleimide compounds with an absorption wavelength of 475 nm or less are more preferred, and maleimide compounds with an absorption wavelength of 450 nm or less are even more preferred. By matching the absorption characteristics of the maleimide compound with the emission wavelength of the (B) exhausted emission (OSL) material, the efficiency of the polymerization reaction can be increased.

[0014] Examples of bismaleimide compounds include N,N'-(4,4'-diphenylmethane)bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, bis-(3-ethyl-5-methyl-4-maleimoidphenyl)methane, m-phenylene bismaleimide (N,N'-1,3-phenylene bismaleimide), 1,6-bismaleimide hexane, and 1,2-bismaleimide ethane (N,N'-ethyl Examples include, but are not limited to, dimaleimide, N,N'-(1,2-phenylene)bismaleimide, N,N-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N,N'-(sulfonyldi-p-phenylene)dimaleimide, N,N'-[3,3'-(1,3-phenylenedioxy)diphenyl]bismaleimide, N,N'-[4,4'-(1,3-phenylenedioxy)diphenyl]bismaleimide, and 4,4'-dimaleimide phenyl ether. These may be used individually or in combination of two or more.

[0015] When a low room-temperature modulus is required for the cured resin composition, the bismaleimide compound is preferably a bismaleimide having hydrocarbon groups derived from dimer acid. Such bismaleimides are described, for example, in Japanese Patent Application Publication No. 2015-193725. Examples of commercially available bismaleimides having hydrocarbon groups derived from dimer acid include, but are not limited to, "BMI-689", "BMI-1500", "BMI-1700", which are liquid at 25°C, or "BMI-3000", which is solid at 25°C (all manufactured by Designer Molecules Inc.). These may be used individually or in combination of two or more.

[0016] Examples of monofunctional maleimide compounds include, but are not limited to, monofunctional aliphatic maleimide compounds such as Nn-butylmaleimide, N-hexylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-propyl carbonate, and N-ethyl-(2-maleimidoethyl)carbamate; alicyclic monofunctional maleimide compounds such as N-cyclohexylmaleimide; N-arylmaleimides such as N-phenylmaleimide; and N-aralkylmaleimides such as N-benzylmaleimide. The aliphatic and alicyclic maleimides may have substituents, such as phenyl groups, benzyl groups, and hydroxyl groups. The N-arylmaleimides and N-aralkylmaleimides may also have substituents, such as alkyl groups, nitro groups, hydroxyl groups, alkoxy groups, carboxyl groups, and halogen groups. These may be used individually or in combination of two or more. Commercially available single-tube maleimide products include, for example, Imilex. (R) -C, Imilex (R) Examples include -P (both manufactured by Nippon Shokubai Co., Ltd.) and O-CPMI (manufactured by Yamato Kasei Kogyo Co., Ltd.), but are not limited to these.

[0017] In this specification, a (meth)acrylate compound is a compound having at least one (meth)acryloyl group in its molecule, and includes monofunctional (meth)acrylate compounds having one (meth)acryloyl group and polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups. Examples of monofunctional (meth)acrylate compounds include: -Ethyl (meth)acrylate, trifluoroethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, glycidyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxypolyethylene Esters of monohydric alcohols and (meth)acrylic acid, such as glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, 2-ethylhexyldiethylene glycol (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, 3-phenoxybenzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, octyl acrylate, nonyl acrylate, isononyl acrylate, 3,3,5-Trimethylcyclohexyl acrylate, cyclic trimethylolpropane formal acrylate, 1-naphthalene methyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, noni Phenoxypolyethylene glycol (meth)acrylate, tetrahydrodicyclopentadienyl (meth)acrylate, 2-(o-phenylphenoxy)ethyl (meth)acrylate, isobornylcyclohexyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 1-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, 2-methyl-2-adamantanyl (meth)acrylate, 2- Ethyl-2-adamantanyl (meth)acrylate, 2-isopropyladamantan-2-yl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, (adamantan-1-yloxy)methyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 1-methyl-1-ethyl-1-adamantylmethanol (meth)acrylate, 1,1-diethyl-1-adamantylmethanol (meth)acrylate, 2-cyclohexylpropane-2-yl (meth)acrylate, 1-isopropylcyclohexyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, 1-methylcyclohexyl (meth)acrylate, tetrahydropyranyl (meth)acrylate, tetrahydro-2-furanyl (meth)acrylate, 2-oxotetrahydrofuran-3-yl (meth)acrylate, (5-oxotetrahydrofuran-2-yl)methyl (meth)acrylate, (2-oxo-1,Examples include, but are not limited to, mono(meth)acrylates of polyhydric alcohols or esters of monohydric alcohols and (meth)acrylic acid, such as 3-dioxolan-4-yl)methyl(meth)acrylate, N-acryloyloxyethylhexahydrophthalimide, α-acryloyl-ω-methoxypoly(oxyethylene), and 1-ethoxyethyl(meth)acrylate. These may be used individually or in combination of two or more. Examples of polyfunctional (meth)acrylate compounds include di(meth)acrylate of tris(2-hydroxyethyl) isocyanurate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, or their oligomers; pentaerythritol tri(meth)acrylate, or its oligomers; poly(meth)acrylate of dipentaerythritol; tris(acryloxyethyl) isocyanurate; caprolactone-modified tris((meth)acryloxyethyl) isocyanurate; alkyl-modified poly(meth)acrylate of dipentaerythritol; poly(meth)acrylate of caprolactone-modified dipentaerythritol; etoxy Examples include, but are not limited to, bisphenol A cide di(meth)acrylate; dihydrocyclopentadiethyl(meth)acrylate, as well as polyester(meth)acrylate, dimethylol-tricyclodecane di(meth)acrylate, ditrimethylolpropane poly(meth)acrylate, polyurethane having two or more (meth)acryloyl groups in one molecule, polyester having two or more (meth)acryloyl groups in one molecule, phenoxyethyl(meth)acrylate, isobornyl(meth)acrylate, phenoxydiethylene glycol(meth)acrylate, 4-tert-butylcyclohexyl(meth)acrylate, epoxy resin half(meth)acrylate, etc. The (meth)acrylate compound may be any one of the (meth)acrylate compounds mentioned above, or two or more may be used in combination. Examples of commercially available (meth)acrylate compounds include, but are not limited to, polyester acrylate (product name: EBECRYL810) manufactured by Daicel Ornex Co., Ltd., ditrimethylolpropanetetraacrylate (product name: EBECRYL140) manufactured by Daicel Ornex Co., Ltd., polyester acrylate (product name: M7100) manufactured by Toagosei Co., Ltd., dimethylol-tricyclodecanediaacrylate (product name: Light Acrylate DCP-A) manufactured by Kyoeisha Chemical Co., Ltd., and neopentyl glycol-modified trimethylolpropanediaacrylate (product name: Kayarad R-604) manufactured by Nippon Kayaku Co., Ltd.

[0018] (Meth)acrylamide compounds are compounds having at least one acrylamide group (H2C=CHCONH-) or methacrylamide group ((H2C=C(CH3)CONH-). Examples of (meth)acrylamide compounds include, but are not limited to, N,N'-methylenebis(meth)acrylamide, N,N'-ethylenebis(meth)acrylamide, and 1,2-di(meth)acrylamide ethylene glycol.

[0019] Known cyanoacrylate compounds represented by H2C=C(CN)-COOR can be used. In this formula, R is an ester residue such as an alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, or aryl group. The number of carbon atoms in the ester residue is not particularly limited, but typically those with 1 to 8 carbon atoms can be used. Ester residues consisting of substituted hydrocarbon groups such as alkoxyalkyl groups and trialkylsilylalkyl groups can also be used. Examples of cyanoacrylate compounds include, but are not limited to, alkyl and cycloalkyl cyanoacrylates such as methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, and cyclohexyl cyanoacrylate; alkenyl and cycloalkenyl cyanoacrylates such as allyl cyanoacrylate, methallyl cyanoacrylate, and cyclohexenyl cyanoacrylate; alkynyl cyanoacrylates such as propangyl cyanoacrylate; aryl cyanoacrylates such as phenyl cyanoacrylate and toluyl cyanoacrylate; methoxyethyl cyanoacrylate, ethoxyethyl cyanoacrylate, and furfuryl cyanoacrylate containing heteroatoms; trimethylsilylmethyl cyanoacrylate, trimethylsilylethyl cyanoacrylate, trimethylsilylpropyl cyanoacrylate, and dimethylvinylsilylmethyl cyanoacrylate containing silicon. These can be used individually, or two or more can be used in combination.

[0020] Vinyl ether compounds are compounds having at least one vinyl ether group (H2C=CH-O-). Examples of vinyl ether compounds include, but are not limited to, ethyl vinyl ether, triethylene glycol divinyl ether, trimethylolpropane trivinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 1,4-butanediol divinyl ether, nonanediol divinyl ether, cyclohexanediol divinyl ether, and cyclohexanedimethanol divinyl ether. These may be used individually or in combination of two or more.

[0021] Styrene compounds are compounds having at least one styrene group (H2C=CH-C6H5-). Examples of styrene compounds include, but are not limited to, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-t-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, N,N-diethyl-4-aminoethylstyrene, and 4-methoxystyrene. These may be used individually or in combination of two or more.

[0022] Methylene malonates are malonates having at least one methylene group in their molecule, and include monofunctional methylene malonates having one methylene group and polyfunctional methylene malonates having two or more methylene groups. Methylene malonates preferably have a molecular weight of 220 or higher. There are no particular restrictions on the types of methylene malonates that can be used; in addition to compounds described in WO2018 / 212330A1, etc., various disclosed methylene malonates can be used. Methylene malonates may be used individually or in combination of two or more types.

[0023] In a mixture of a compound having an unsaturated double bond and a thiol compound, the thiol compound is a compound containing at least one thiol group, and this thiol group can undergo a radical addition reaction (en-thiol reaction) with the unsaturated double bond of the compound having the unsaturated double bond. Thiol compounds are broadly classified into thiol compounds that have hydrolyzable substructures such as ester bonds in their molecule (i.e., hydrolyzable) and thiol compounds that do not have such substructures (i.e., non-hydrolyzable). Examples of hydrolyzable thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: TMMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (manufactured by SC Organic Chemicals Co., Ltd.: TEMPIC), pentaerythritol tetrakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: PEMP), and tetraethylene glycol bis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: EGMP- 4) Examples include, but are not limited to, dipentaerythritol hexakis(3-mercaptopropionate) (manufactured by SC Organic Chemicals Co., Ltd.: DPMP), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Resonaq Corporation: Karenz MT® PE1), and 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Resonaq Corporation: Karenz MT® NR1). These may be used individually or in combination of two or more. Examples of non-hydrolyzable polyfunctional thiol compounds include 1,3,4,6-tetrakis(2-mercaptoethyl) glycoluryl (manufactured by Shikoku Chemicals, Inc.: TS-G), 1,3,4,6-tetrakis(3-mercaptopropyl) glycoluryl (manufactured by Shikoku Chemicals, Inc.: C3 TS-G), 1,3,4,6-tetrakis(mercaptomethyl) glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a-methyl glycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-dimethyl glycoluryl, and 1,3,4,6-tetraki Su(2-mercaptoethyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-dimethylglycoluryl, 1,3,4,6-tetrakis(mercaptomethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(2-mercaptoethyl)-3a,6a-diphenylglycoluryl, 1,3,4,6-tetrakis(3-mercaptopropyl)-3a,6a-diphenylglycoluryl, Tris(3-mercaptopropyl)isocyanurate, 1,3,5-tris[3-(2-mercaptoethylsulfanyl)propyl]isocyanurate, 1,3,5-tris[2-(3-mercaptopropoxy)ethyl]isocyanurate, pentaerythritol tripropanthol (manufactured by SC Organic Chemicals Co., Ltd.: PEPT), 3-[2,3-bis(3-sulfanylpropoxy)propoxy]propane-1-thiol, 1,2,3-tris(3-mercaptopropoxy)propane , 3-[2,2-bis[(3-mercaptopropoxy)methyl]butoxy]-1-propanthol, pentaerythritol tetrapropanthol, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-Trithiaundecane, 4,7-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, 4,8-Dimercaptomethyl-1,11-Dimercapto-3,6,9-Trithiaundecane, Tetrakis(mercaptomethylthiomethyl)methane, Tetrakis(2-mercaptoethylthiomethyl)methane, Tetrakis(3-mercaptopropylthiomethyl)methane, 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 1,1,2,2-Tetrakis(mercaptomethylthio)ethane, 1,1,5,5-Tetrakis( Mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiahexane, 2,2-bis(mercaptomethylthio)ethanethiol, 3-mercaptomethylthio-1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio )-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio)ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexakis(mercaptomethylthio) )-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,13,14-hexakis(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-Hexatiahexadecane, 8-[bis(mercaptomethylthio)methyl]-3,4,12,13-tetrakis(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexatiapentadecane, 4,6-bis[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-1,3-dithiane, 4-[3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio]-6-mercaptomethylthio-1,3-dithiane, 1,1-bis[4-(6-mercaptomethylthio] [Tomethylthio)-1,3-Dithianylthio]-1,3-Bis(mercaptomethylthio)propane, 1-[4-(6-mercaptomethylthio)-1,3-Dithianylthio]-3-[2,2-Bis(mercaptomethylthio)ethyl]-7,9-Bis(mercaptomethylthio)-2,4,6,10-Tetrathiaundecane, 3-[2-(1,3-Dithiethanyl)]methyl-7,9-Bis(mercaptomethylthio)-1,11-Dimercapto-2,4,6,10-Tetrathiaundecane, 9-[2-(1,3-Dithiethanyl)]methyl-3,5,13,1 5-Tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-[2-(1,3-dithiethanyl)]methyl-7,9,13,15-Tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 4,6-bis[4-(6-mercaptomethylthio)-1,3-dithianylthio]-6-[4-(6-mercaptomethylthio)-1,3-dithianylthio]-1,3-dithiane, 4-[3,4,8,9-Tetrakis(M Lucaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl]-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-1,3-dithiolane, 4-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]-5-mercaptomethylthio-1,3-dithiolane, 4-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-Trithiaoctyl]-5-mercaptomethylthio-1,3-dithiolane, 2-{bis[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]methyl}-1,3-dithiethane, 2-[3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio]mercaptomethylthiomethyl-1,3-dithiethane, 2-[3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto- Examples of difunctional thiol compounds disclosed in WO2019 / 082962, such as 2,4,7-trithiaoctyl]mercaptomethylthiomethyl-1,3-dithiethane, 4-{1-[2-(1,3-dithiethanyl)]-3-mercapto-2-thiapropylthio}-5-[1,2-bis(mercaptomethylthio)-4-mercapto-3-thiabutylthio]-1,3-dithiolane, 2,2'-[cyclohexylidenebis(thio-2,1-ethanediylthio)]bis[ethanethiol], and 4,4'-[(1,3-phenylene)bis(oxy)]bis[1-butanethiol], as well as dimers, trimers, and tetramers of the thiol compounds, can be cited, but are not limited to these. These may be used individually or in combination of two or more.

[0024] Cationic polymerizable compounds are compounds having one or more cationic polymerizable groups in their molecule. Examples of cationic polymerizable compounds include, but are not limited to, compounds having epoxy groups, compounds having oxetanyl groups, compounds having vinyl ether groups, compounds having other cationic polymerizable groups, and compounds having any combination of these cationic polymerizable groups.

[0025] In this specification, a compound having an epoxy group is a compound having at least one epoxy group in its molecule, and is also referred to as an epoxy compound. Examples include monofunctional epoxy compounds having one epoxy group and polyfunctional epoxy compounds having two or more epoxy groups. In one embodiment, the epoxy compound preferably contains at least a polyfunctional epoxy compound, and may contain a combination of a polyfunctional epoxy compound and a monofunctional epoxy compound. Epoxy compounds can be broadly classified into epoxy compounds having an aromatic ring skeleton, aliphatic epoxy compounds, and alicyclic epoxy compounds, depending on the type of skeleton.

[0026] In this specification, a compound having an oxetanyl group is a compound having at least one oxetane ring (e.g., a 3-oxetanyl group) in its molecule, and is also referred to as an oxetane compound. In one embodiment, the oxetane compound preferably has 1 to 6 oxetanyl groups in its molecule, and more preferably has 1 to 2 oxetanyl groups in its molecule.

[0027] In this specification, a compound having a vinyl ether group is a compound having at least one vinyl ether group in its molecule.

[0028] Specific examples of cationic polymerizable compounds include glycidyl ethers of tetra(hydrophenyl)alkanes, glycidyl ethers of tetrahydroxybenzophenone, epoxidized polyvinylphenol, p-tert-butylphenyl glycidyl ether, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,2-epoxytetradecane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, and 6-methyl-3,4-e Poxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), pro Pan-2,2-diyl-bis(3,4-epoxycyclohexane), 2,2-bis(3,4-epoxycyclohexyl)propane, dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexanecarboxylate), limonene dioxide (1,2:8,9-diepoxylimonene), (3,3',4,4'-diepoxy)bicyclohexyl, dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,Compounds in which some or all of the double bonds of 2-epoxy-2-epoxyethylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, α-pinene oxide, 1,2-epoxy-4-(2-oxyranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol, epoxidized polybutadiene, styrene-butadiene copolymers are epoxidized, bis[1-ethyl(3-oxetanyl)]methyl ether (also known as (3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl Oxetane, xylylene bisoxetane, 4,4'-bis[3-ethyl-(3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis(3-ethyl-3-oxetanylmethoxy)methylbenzene, (bis[(3-ethyl-3-oxetanyl)methyl]isophthalate), 3-ethyl-3-hydroxymethyl oxetane, 2-ethylhexyl oxetane, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-[(2-ethylhexyloxy)methyl]oxetane, 3-ethyl-3- Examples include, but are not limited to, (4-hydroxybutyl)oxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, oxetanylsilsesquioxetane, 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane, phenol novolac oxetane, 1,4-butanediol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 2-(2-vinyloxyethoxy)ethyl acrylate, 2-(2-vinyloxyethoxy)ethyl methacrylate, 1,4-cyclohexanedimethanol monovinyl ether, and 1,4-cyclohexanedimethanol divinyl ether.

[0029] Commercially available cationic polymerizable compounds include EPICLON® 850, 850-S, EXA-850CRP, EXA-8067 from DIC Corporation; AER9000 from Asahi Kasei Corporation; EP-4000S, EP-4003S, EP-4010S from ADEKA Corporation; EPICLON® 830-S, EXA-830LVP, EXA-835LV from DIC Corporation; and EPICLON® HP-40 from DIC Corporation. 32D, HP-720H; EPICLON® N-740, N-770 manufactured by DIC Corporation; EPICLON® N-660, N-670, N-655-EXP-S manufactured by DIC Corporation; Adekaglycirol® ED-509E, ED-509S manufactured by ADEKA Corporation; OPP-G manufactured by Sanko Co., Ltd.; Epolite 100MF manufactured by Kyoeisha Chemical Co., Ltd.; AER-9000 manufactured by Asahi Kasei Corporation; jER manufactured by Mitsubishi Chemical Corporation Examples include, but are not limited to, YX7400N; jER YX8000 manufactured by Mitsubishi Chemical Corporation; Celoxide® 2021P manufactured by Daicel Corporation; Celoxide® 8010 manufactured by Daicel Corporation; EHPE3150 manufactured by Daicel Corporation; EPOLEAD PB manufactured by Daicel Corporation; EPOFRIEND manufactured by Daicel Corporation; HiREM-1 and HiREM-2 manufactured by Shikoku Chemicals, Inc.; OXT-191 manufactured by Toagosei Co., Ltd.; OXT-221 manufactured by Toagosei Co., Ltd.; and PHOX manufactured by Toagosei Co., Ltd.

[0030] Any one cationic polymerizable compound may be used, or two or more may be used in combination.

[0031] Examples of anionic polymerizable compounds include epoxy group compounds, as shown in the examples of cationic polymerizable compounds, and their curing agents, such as thiol-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, and amine-based curing agents. Methylene malonates, as shown in the examples of radical polymerizable compounds, can also be cited as anionic polymerizable compounds. Furthermore, (meth)acrylate compounds, as shown in the examples of radical polymerizable compounds, can also be cited as anionic polymerizable compounds when used in combination with thiol compounds. These may be used individually or in combination of two or more.

[0032] (A) The polymerizable compound may be any one of the following: a radical polymerizable compound, a cationic polymerizable compound, or an anionic polymerizable compound, or any combination of these may be used.

[0033] The content of polymerizable compound (A) in the photocurable resin composition may be 1 to 99 parts by mass per 100 parts by mass of the total amount of the photocurable resin composition. In one embodiment, the content of polymerizable compound (A) in the photocurable resin composition is preferably 5 to 50 parts by mass, and more preferably 7 to 30 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition. In this embodiment, the photocurable resin composition can be cured by photocuring alone, even if there are many obstructing materials such as fillers. In another embodiment, the content of polymerizable compound (A) in the photocurable resin composition is preferably 30 to 99 parts by mass, more preferably 50 to 99 parts by mass, and even more preferably 60 to 99 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition. Furthermore, the content of polymerizable compound (A) in the photocurable resin composition is preferably 75 to 99 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 98 parts by mass, based on 100 parts by mass of the total amount of organic matter contained in the photocurable resin composition (excluding low-stress imparting materials such as organic fillers and elastomers). Furthermore, the amount of component (A) is preferably 75 to 99.9 parts by mass, more preferably 80 to 99.5 parts by mass, and even more preferably 85 to 99 parts by mass, based on 100 parts by mass of the total of components (A) and (B), or based on 100 parts by mass of the total of components (A), (B), and (C).

[0034] (B) Exhausted Luminescence (OSL) Materials The photocurable resin composition of this embodiment includes (B) exhausted luminescence (OSL) material (hereinafter also referred to as "component (B)"). When the exhausted luminescence (OSL) material is irradiated with stimulating light of a specific wavelength while in a state in which excitation energy has been accumulated, it generates the accumulated energy as OSL. By including this exhausted luminescence (OSL) material in the resin composition together with a maleimide compound and / or (C) a photopolymerization initiator described later, and irradiating the resin composition with long-wavelength stimulating light, the exhausted luminescence (OSL) material generates short-wavelength OSL inside the resin composition, activating the maleimide compound and / or the photopolymerization initiator, and curing the resin composition. In one embodiment, it is preferable that the (B) exhausted luminescence (OSL) material is configured to exhibit exhausted luminescence including wavelengths less than 500 nm when irradiated with stimulating light with a wavelength of 500 nm or more. (A) An exhausted luminescence (OSL) material used to cure a polymerizable compound is another embodiment of the present invention. The use of exhausted luminescence (OSL) material for curing (A) polymerizable compounds is also another aspect of the present invention. A method for curing (A) polymerizable compounds, comprising the use of exhausted luminescence (OSL) material, is also another aspect of the present invention.

[0035] In one embodiment, (B) the exhausted luminescence (OSL) material is preferably a material that exhibits exhausted luminescence including wavelengths less than 500 nm when irradiated with stimulating light with a wavelength of 500 nm or more, more preferably a material that exhibits exhausted luminescence including wavelengths of 450 nm or less, and even more preferably a material that exhibits exhausted luminescence including wavelengths of 430 nm or less. In one embodiment, (B) the exhausted luminescence (OSL) material is a material that exhibits exhausted luminescence including (near) ultraviolet light wavelengths (200 nm to 380 nm) when irradiated with stimulating light with a wavelength of 500 nm or more.

[0036] In one embodiment, the stimulation wavelength of the (B) exhausted luminescence (OSL) material is preferably longer than the emission wavelength of the (B) exhausted luminescence (OSL) material, for example, a wavelength of 500 nm or more, for example, a wavelength in the range of 500 nm to 2000 nm.

[0037] In this embodiment, the optically stimulated luminescence (OSL) material may be any as long as it is configured to generate optically stimulated luminescence including wavelengths less than 500 nm by irradiating stimulation light with a wavelength of 500 nm or more, and may be either an inorganic optically stimulated luminescence (OSL) material or an organic optically stimulated luminescence (OSL) material.

[0038] The inorganic optically stimulated luminescence (OSL) material has a wide bandgap, and an impurity element that forms a luminescence center and / or an electron trapping center is doped into a host material (inorganic ceramics) having a large gap between the valence band (VB) and the conduction band (CB), thereby exhibiting optically stimulated luminescence characteristics. In the inorganic optically stimulated luminescence (OSL) material, by appropriately selecting the type and crystallinity of the inorganic ceramics as the host material, and the type and introduction amount (doping amount) of the contained impurity elements, optically stimulated luminescence of an arbitrary wavelength can be obtained. In one embodiment, the optically stimulated luminescence (OSL) material is an inorganic ceramics containing an impurity element that forms a luminescence center and / or an electron trapping center, and the inorganic ceramics is an oxide or a halide containing at least one metal element selected from the group consisting of an alkali metal, an alkaline earth metal, a rare earth metal, and a rare earth metal. The inorganic ceramics may contain a non-metal element or a semi-metal element such as phosphorus (P) or silicon (Si). Specific examples of such inorganic ceramics include LaPO4, YPO4, GdPO4, Y3Al5O 12 、Y2GdAl3O 12 、YGd2Al3O 12 、Y3Al3Ga2O 12, LiYSiO4, LiYGeO4, LiGdSiO4, LiGdGeO4, NaYSiO4, NaYGeO4, NaGdGeO4, LiYSiO4, LiCaPO4, LiMgPO4, NaMgPO4, NaCaPO4, NaSrPO4, NaBaPO4, LiTaO3, BaFBr, NaCl, LiF, NaMgF3, NaMgF3, β-Sr2SiO4, KMgF3, Cs2LiYCl6, Li3YCl6, YAlO3, GdAlO3, LiYF4, YF3, Al2O3, Y2SiO5, α-Y2Si2O7, β-Y2Si2O7, γ-Y2Si2O7, etc. are included, but are not limited thereto.

[0039] In one embodiment, the impurity element forming the emission center is at least one selected from the group consisting of cerium (Ce), praseodymium (Pr), europium (Eu), thulium (Tm), bismuth (Bi), and carbon (C), and the impurity element forming the electron trapping center is titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and carbon (C). These impurity elements can exist as ions in the optically stimulated luminescence (OSL) material. Impurity elements such as cerium (Ce), praseodymium (Pr), europium (Eu), thulium (Tm), and carbon (C) may be of a single type and perform both functions of the emission center and the electron trapping center. In one embodiment, the molar ratio (cation: x: y) of the impurity element x forming the emission center to the impurity element y forming the electron trapping center with respect to all cations in the OSL material preferably satisfies x + y < 1, 0.0001 < x < 1, and 0.00001 < y < 1, and is 1 - x - y: x: y. The molar ratio (x: y) of the impurity element x forming the emission center to the impurity element y forming the electron trapping center is preferably 1: 0.1 to 10.

[0040] In one embodiment, the exhausted luminescence (OSL) material is (La0.99Ce0.005Dy0.005)PO4. In one embodiment, the exhausted luminescence (OSL) material is (Y0.99Ce0.005Nd0.005)PO4. In one embodiment, the exhausted luminescence (OSL) material is (La0.993Ce0.005Dy0.002)PO4. In one embodiment, the exhausted luminescence (OSL) material is (Y0.99Ce0.005Dy0.005)PO4. In one embodiment, the exhausted luminescence (OSL) material is (La0.99966Ce0.00017Dy0.00017)PO4.

[0041] Inorganic OSL (Optical System Luminescence) materials can be manufactured by known methods, such as solid-phase reaction methods, coprecipitation methods, sol-gel methods (complex polymerization methods), and solvothermal methods (hydrothermal methods). Solid-phase reaction is a method of producing a target product by mixing raw materials and then firing them at a high temperature. For example, when producing phosphate-based exhausted luminescence (OSL) materials by solid-phase reaction, the following can be done: For the metal oxide that serves as the raw material for the metal element contained in the inorganic ceramic as the base material, weigh out the oxide of the impurity element that will serve as the luminescence center so that it is 0.001 mol% to 10 mol%, and weigh out the oxide of the impurity element that will serve as the electron-trapping center so that it is 0.001 mol% to 1 mol%. Weigh out ammonium dihydrogen phosphate in a molar ratio of 1:1 to the total amount of metal element and impurity element contained in these raw materials. Mix these raw materials, place them in an alumina vessel, and fire them in an air atmosphere at a temperature of 1000°C to 1400°C for 4 to 12 hours to obtain phosphate-based exhausted luminescence (OSL) materials. Coprecipitation is a method of obtaining an extremely homogeneous mixture by dissolving two or more elements in some medium and then precipitating them. For example, when producing phosphate-based exhausted luminescence (OSL) materials by coprecipitation, the following can be done: Weigh out nitrates of impurity elements that will become luminescence centers, in an amount of 0.001 mol% to 10 mol%, and nitrates of impurity elements that will become electron-trapping centers, in an amount of 0.001 mol% to 1 mol%, relative to the metal nitrates that will serve as raw materials for the metal elements contained in the inorganic ceramics used as the base material. Dissolve these raw materials in distilled water, add 0.1 mol% to 10 mol% citric acid relative to the total amount of metal and impurity elements contained in these raw materials and mix. Then, add an aqueous phosphoric acid solution dropwise in a 1:1 molar ratio relative to the total amount of metal and impurity elements contained in these raw materials. The obtained precipitate product is filtered, washed, and dried, then placed in an alumina vessel and calcined in an air atmosphere at a temperature of 600°C to 1000°C for 2 to 6 hours to obtain a phosphate-based luminescent (OSL) material. For the sol-gel method, see, for example, the method described in H. Nakamura, et al., RSC Adv. 10 (2020) 12535-12546. The solvothermal process is a general term for methods of synthesizing compounds or growing crystals by dissolving and eluting starting materials using a liquid or supercritical solvent as the reaction field. When water is used as the solvent, it is called the hydrothermal process.

[0042] Any one type of exhaustible luminescence (OSL) material may be used, or two or more types may be used in combination. For example, in one embodiment, by using two or more types of exhaustible luminescence (OSL) materials in combination, energy transfer from one OSL material to another becomes possible within the resin composition. Through such stepwise energy transfer, the emission wavelength of the OSL material can be adjusted so that it ultimately includes wavelengths less than 500 nm from the desired stimulation light, thereby enabling photocuring of the resin composition using the desired stimulation light.

[0043] The content of (B) exhausted luminescence (OSL) material in the photocurable resin composition is preferably 0.05 to 95 parts by mass, more preferably 0.1 to 50 parts by mass, and even more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the total amount of the photocurable resin composition, from the viewpoint of photocuring degree.

[0044] The photocurable resin composition of this embodiment satisfies at least one of the following features (a) and (b): (a)(A) The polymerizable compound includes a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. The maleimide compound and (C) the photopolymerization initiator are activated by (B) the exhausted luminescence (OSL) material, which generates OSL with wavelengths less than 500 nm, generating active species such as radicals, cations, and anions, thereby promoting the polymerization of the polymerizable compound. This provides a photocurable resin composition that can be cured by light irradiation alone. In this specification, the maleimide compound and (C) the photopolymerization initiator may be collectively referred to as the "initiator".

[0045] In feature (a) described above, the maleimide compound is activated by (B) exhausted luminescence (OSL) material with a wavelength of less than 500 nm, particularly 450 nm or less, generating radicals and promoting the polymerization of the radical polymerizable compound. That is, the maleimide compound is both a polymerizable compound and can function as a photoradical polymerization initiator, and promotes the polymerization of the radical polymerizable compound, including the maleimide compound itself, even without containing a separate (C) photopolymerization initiator. When feature (a) described above is satisfied, the (A) polymerizable compound may include radical polymerizable compounds other than the maleimide compound. Furthermore, when feature (a) described above is satisfied, the photocurable resin composition may further contain a (C) photopolymerization initiator (feature (b) described above). When the above characteristic (a) is satisfied, the amount of maleimide compound in the photocurable resin composition is preferably 0.1 to 100 parts by mass, and more preferably 0.2 to 100 parts by mass, based on 100 parts by mass of the total radical polymerizable compounds (i.e., the sum of the maleimide compound and other radical polymerizable compounds), from the viewpoint of photoirradiation reactivity.

[0046] (C) Photopolymerization initiator The photocurable resin composition of this embodiment that satisfies the above-mentioned feature (b) contains (C) a photopolymerization initiator (hereinafter also referred to as "component (C)"). A photopolymerization initiator is a reactant that absorbs light to generate active species such as radicals, cations, and anions, thereby promoting the polymerization of a polymerizable compound. In one embodiment, the (C) photopolymerization initiator is activated by OSL with a wavelength of less than 500 nm generated by the (B) exhausted luminescence (OSL) material, thereby generating active species. The (C) photopolymerization initiator is more preferably activated by light with a wavelength of 450 nm or less, and even more preferably activated by light with a wavelength of 430 nm or less. By matching the absorption characteristics of the (C) photopolymerization initiator with the emission wavelength of the (B) exhausted luminescence (OSL) material, the efficiency of the polymerization reaction can be increased. The (C) photopolymerization initiator can be appropriately selected from a photoradical polymerization initiator, a photoacid generator, a photobase generator, or any combination thereof.

[0047] Photoradical polymerization initiators absorb light and generate radicals as active species, thereby promoting the polymerization of radically polymerizable compounds. Examples of photoradical polymerization initiators include, but are not limited to, alkylphenone compounds, acylphosphine oxide compounds, oxime ester compounds, and compounds having a photosensitive site and a peroxide structure.

[0048] Examples of alkylphenone compounds include benzyldimethyl ketals such as 2,2-dimethoxy-1,2-diphenylethane-1-one (commercially available as Omnirad 651 from IGM Resins BV); α-aminoalkylphenones such as 2-methyl-2-morpholino(4-thiomethylphenyl)propan-1-one (commercially available as Omnirad 907 from IGM Resins BV); α-hydroxyalkylphenones such as 1-hydroxycyclohexylphenyl ketone (commercially available as Omnirad 184 from IGM Resins BV); 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (commercially available as Omnirad 379EG from IGM Resins BV); and 2-benzyl-2-(dimethylamino)-4'-morpholinbutyrophenone (commercially available as IGM Resins Examples include, but are not limited to, the Omnirad 369 manufactured by BV. These may be used individually or in combination of two or more.

[0049] Examples of acylphosphine oxide compounds include, but are not limited to, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (commercially available as Omnirad TPO H from IGM Resins BV) and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available as Omnirad 819 from IGM Resins BV). These may be used individually or in combination of two or more.

[0050] Examples of oxime ester compounds include, but are not limited to, 1,2-octanedione,1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime) (trade name: Irgacure OXE-02, manufactured by BASF), and methanone,ethanone,1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-,1-(O-acetyl oxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA). These may be used individually or in combination of two or more.

[0051] Examples of compounds having a photosensitive site and a peroxide structure, or commercially available products thereof, include, but are not limited to, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone (BTTB), Perdual TA, and Perdual TX (all manufactured by NOF Corporation).

[0052] In addition to the photoradical polymerization initiators mentioned above, other examples of photoradical polymerization initiators include 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, and benzyldimethyl Examples include, but are not limited to, ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, and camphorquinone. These may be used individually or in combination of two or more.

[0053] Any one type of photoradical polymerization initiator may be used, or two or more types may be used in combination.

[0054] From the viewpoint of photoirradiation reactivity, the content of the photoradical polymerization initiator in the photocurable resin composition is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 8 parts by mass, per 100 parts by mass of the total radical polymerizable compounds.

[0055] A photoacid generator absorbs light and generates acid as an active species, thereby promoting the polymerization of cationic polymerizable compounds. Various compounds described in Japanese Patent Publication No. 2022-080366 can be used as photoacid generators, and are not particularly limited. A preferred acid generator is BF4. - SbF6-, AsF6 - , B(C6F5)4 - Ga(C6F5)4 - , C(CF3SO2)3 - [P(R 1 ) a F 6-a ] - [C(R 1 SO2)3] - , or [N(R 1 SO2)2] - (In the formula, R 1 Each of these is an alkyl group in which at least some of the hydrogen atoms are replaced by fluorine atoms, and a is an integer from 0 to 5. If a is an integer of 2 or more, there are multiple R groups. 1 Various onium salts are available, in which the counter anions are iodonium cations, sulfonium cations, ammonium cations, and phosphonium cations, etc., and the cation moiety is iodonium cation, sulfonium cation, ammonium cation, etc., and these may be the same or different from each other.

[0056] Examples of iodonium cations include iodonium ions such as diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, and 4-isobutylphenyl(p-tolyl)iodonium.

[0057] Examples of sulfonium ions include triphenylsulfonium, tri-p-tolylsulfonium, tri-o-tolylsulfonium, tris(4-methoxyphenyl)sulfonium, 1-naphthyldiphenylsulfonium, 2-naphthyldiphenylsulfonium, tris(4-fluorophenyl)sulfonium, tri-1-naphthylsulfonium, tri-2-naphthylsulfonium, tris(4-hydroxyphenyl)sulfonium, 4-(phenylthio)phenyldiphenylsulfonium, 4-(p-tolylthio)phenyldi-p-tolylsulfonium, 4-(4-methoxyphenylthio)phenylbis(4-methoxyphenyl)sulfonium, and 4-(phenylthio)phenylbis(4-fluorophenyl (L)sulfonium, 4-(phenylthio)phenylbis(4-methoxyphenyl)sulfonium, 4-(phenylthio)phenyldi-p-tolylsulfonium, [4-(4-biphenylylthio)phenyl]-4-biphenylylphenylsulfonium, [4-(2-thiooxantonylthio)phenyl]diphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methylphenyl)sulfonio]phenyl}sulfide, bis{4-[bis(4-methoxyphenyl)sulfonio] Phenyl sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyldiphenylsulfonium, 4-(4-benzoylphenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-Dihydroanthracene-2-yldiphenylsulfonium, 2-[(di-p-tolyl)sulfonio]thioxanthone, 2-[(diphenyl)sulfonio]thioxanthone, 4-(9-oxo-9H-thioxanthene-2-yl)thiophenyl-9-oxo-9H-thioxanthene-2-ylphenylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-[4-(4-t-butylbenzoyl)phenylthio]phenyl Examples include triarylsulfonium compounds such as nyldiphenylsulfonium, 4-[4-(benzoylphenylthio)]phenyldi-p-tolylsulfonium, 4-[4-(benzoylphenylthio)]phenyldiphenylsulfonium, 5-(4-methoxyphenyl)thiaanthurenium, 5-phenylthiaanthurenium, 5-tolylthiaanthurenium, 5-(4-ethoxyphenyl)thiaanthurenium, and 5-(2,4,6-trimethylphenyl)thiaanthurenium.

[0058] Examples of ammonium cations include pyrrolidinium such as N,N-dimethylpyrrolidinium, N-ethyl-N-methylpyrrolidinium, and N,N-diethylpyrrolidinium; imidazolinium such as N,N'-dimethylimidazolinium, N,N'-diethylimidazolinium, N-ethyl-N'-methylimidazolinium, 1,3,4-trimethylimidazolinium, and 1,2,3,4-tetramethylimidazolinium; tetrahydropyrimidinium such as N,N'-dimethyltetrahydropyrimidinium; and ammonium cations such as N,N'-dimethylmorpholinium. Examples include piperidinium such as rupholinium and N,N'-diethylpiperidinium, pyridinium such as N-methylpyridinium, N-benzylpyridinium and N-phenacylpyridium, imidazolium such as N,N'-dimethylimidazolium, quinorium such as N-methylquinolium, N-benzylquinolium and N-phenacylquinolium, isoquinolium such as N-methylisoquinolium, thiazonium such as benzylbenzothiazonium and phenacylbenzothiazonium, and acridium such as benzylacridium and phenacylacridium.

[0059] Examples of phosphonium cations include tetraarylphosphoniums such as tetraphenylphosphonium, tetra-p-tolylphosphonium, tetrakis(2-methoxyphenyl)phosphonium, tetrakis(3-methoxyphenyl)phosphonium, and tetrakis(4-methoxyphenyl)phosphonium; triarylphosphoniums such as triphenylbenzylphosphonium, triphenylphenacylphosphonium, triphenylmethylphosphonium, and triphenylbutylphosphonium; and tetraalkylphosphoniums such as triethylbenzylphosphonium, tributylbenzylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetrahexylphosphonium, triethylphenacylphosphonium, and tributylphenacylphosphonium.

[0060] Specific examples of iodonium salt-based photoacid generators include: Photoacid generators that are arcene-type iodonium salts such as diphenyliodonium hexafluoroarsenate, di(4-chlorophenyl)iodonium hexafluoroarsenate, di(4-bromophenyl)iodonium hexafluoroarsenate, and phenyl(4-methoxyphenyl)iodonium hexafluoroarsenate; 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluorophosphate, 4-methylphenyl-4-(1-methylethyl)phenyliodonium tri(pentafluoroethyl)trifluorophosphate (e.g., IK-1 manufactured by Sunapro Co., Ltd.), 4-methylphenyl-4-(2-methylpropyl)phenyliodonium hexafluorophosphate (e.g., IRGACURE® 250 manufactured by BASF), bis(C 10~14 - A photoacid generator that is a phosphate-based iodonium salt such as alkylphenyl)iodonium hexafluorophosphate (e.g., WPI-113 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Photoacid generators that are antimonate-based iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium hexafluoroantimonate (e.g., WPI-116 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Iodonium salt-based photoacid generators such as IK-1FG (manufactured by Sunapro Co., Ltd.); Photoacid generators are borate-type iodonium salts such as 4-methylphenyl-4-(1-methylethyl)phenyliodonium tetrakis(pentafluorophenyl)borate and 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate (e.g., BLUESIL® PI 2074 manufactured by ELKEM SILICONES). These are some examples, but are not limited to these.

[0061] Specific examples of sulfonium salt-based photoacid generators include, but are not limited to, borate-based sulfonium salt photoacid generators (e.g., products manufactured by Sunapro Co., Ltd.: CPI-110B, CPI-310B, CPI-410B, etc., and Omnirad 290, etc., manufactured by IGM Resins BV), phosphate-based sulfonium salt photoacid generators (products manufactured by Sunapro Co., Ltd.: CPI-210S, VC-1S, CPI-410S, etc.), and other sulfonium salt-based photoacid generators (products manufactured by Sunapro Co., Ltd.: CPI-310FG, VC-1FG, etc.).

[0062] You may use one type of photoacid generator, or you may use two or more types in combination.

[0063] The amount of photoacid generator in the photocurable resin composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1 to 15 parts by mass, based on 100 parts by mass of the total amount of cationic polymerizable compounds.

[0064] Photobase generators absorb light and generate bases as active species, thereby promoting the polymerization of anionic polymerizable compounds. Examples of photobase generators include, but are not limited to, various compounds that generate bases such as amines, amidines, guanidines, phosphazenes, and carbenes.Specific examples of photobase generators include, for example, 2-benzyl-2-(dimethylamino)-1-[4-(morpholino)phenyl]-1-butanone, 2-(dimethylamino)-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 2-nitrobenzyl 4-hydroxypiperidine-1-carboxylate, 4,5-dimethoxy-2-nitrobenzyl 2,6-dimethylpiperidine-1-carboxylate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethylcyclohexylcarbamate, 1-(9,10-dioxo-9,10-dihydroanthracene-2-yl)ethyl 1H-imidazole-1-carboxylate, 3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine-1- Ium 2-(3-benzoylphenyl)propanoate, diaminomethaneiminium 2-(3-benzoylphenyl)propanoate, (Z)-N-(((bis(dimethylamino)methylene)amino)(isopropylamino)methylene)propane-2-aminium 2-(3-benzoylphenyl)propanoate, 1,2-dicyclohexyl-4,4,5,5-tetramethylbiguanidium n-butyltriphenylborate, (Z)-{[bis(dimethylamino)methylidene]amino}-N-cyclohexyl(cyclohexylamino)methaniminium tetrakis(3-fluorophenyl)borate, 1,2-diisopropyl-3-[bis(dimethylamino)methylene]guanidium 2-(3-benzoylphenyl)propionate, 9-antrylmethyl Examples include, but are not limited to, N,N-diethylcarbamate, (E)-1-piperidino-3-(2-hydroxyphenyl)-2-propen-1-one, 2-nitrophenylmethyl 4-methacryloyloxypiperidine-1-carboxylate, tetramethylguanidium tetrakis(3-fluorophenyl)borate, tetramethylguanidium tetrakis(4-fluorophenyl)borate, salts containing protonated DBU and tetrakis(3-fluorophenyl)borate anion, and salts containing benzylated DBU and tetrakis(3-fluorophenyl)borate anion. These may be used individually or in combination of two or more.

[0065] Any one type of photobase generator may be used, or two or more types may be used in combination.

[0066] The amount of photobase generator in the photocurable resin composition is preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass, based on 100 parts by mass of the total amount of anionic polymerizable compounds.

[0067] The photopolymerization initiator may be one of the following: a photoradical polymerization initiator, a photoacid generator, or a photobase generator, or any combination of these may be used.

[0068] The photocurable resin composition of this embodiment may optionally contain components (A) and (B) or any other components other than components (A) to (C), such as those described below.

[0069] · Filler The photocurable resin composition of this embodiment may contain fillers to the extent that it does not impair the purpose of this embodiment. By including fillers in the photocurable resin composition, the coefficient of thermal expansion of the cured product obtained by curing the photocurable resin composition can be lowered, improving thermal cycle resistance. Furthermore, if a filler with a low modulus of elasticity is used, the stress generated in the cured product can be alleviated, improving long-term reliability. Fillers are broadly classified into inorganic fillers and organic fillers.

[0070] Inorganic fillers consist of granular bodies formed from inorganic materials and are not particularly limited as long as they have the effect of lowering the coefficient of thermal expansion when added. Examples of inorganic materials include silica, talc, alumina, aluminum nitride, calcium carbonate, aluminum silicate, magnesium silicate, magnesium carbonate, barium sulfate, barium carbonate, lime sulfate, aluminum hydroxide, calcium silicate, potassium titanate, titanium oxide, zinc oxide, silicon carbide, silicon nitride, and boron nitride. One or more inorganic fillers may be used. Silica fillers are preferred because they allow for a higher filling capacity. Amorphous silica is preferred.

[0071] Inorganic fillers are preferably surface-treated with a coupling agent such as a silane coupling agent. This allows the thixotropic index (TI) of the resin composition to be within an appropriate range.

[0072] Examples of organic fillers include polytetrafluoroethylene (PTFE) fillers, silicone fillers, acrylic fillers, and styrene fillers. Organic fillers may also be surface-treated.

[0073] The shape of the filler is not particularly limited and may be spherical, flake-shaped, needle-shaped, irregular, or any other shape.

[0074] The average particle size of the filler is preferably 0.01 to 15 μm, and more preferably 0.01 to 10 μm. From the viewpoint of transmittance of long-wavelength light irradiated onto the photocurable resin composition, the maximum particle size of the filler is preferably 50 μm or less, and more preferably 30 μm or less.

[0075] In this specification, the average particle size is the particle size at 50% of the cumulative value in the volume-based particle size distribution, measured by laser diffraction-scattering. The maximum particle size is the largest particle size in the volume-based particle size distribution, measured by laser diffraction-scattering.

[0076] If a filler is included, the filler content is preferably 0.5 to 80% by mass, and more preferably 1 to 70% by mass, relative to the total mass of the photocurable resin composition.

[0077] • Shaxuhm The photocurable resin composition according to this embodiment may contain a thixotrope, to the extent that it does not impair the effects of this embodiment. Examples of thixotropes include silica such as colloidal silica, hydrophobic silica, fine silica, and nanosilica, as well as bentonite, acetylene black, and Ketjenblack. Nanosilica is preferred from the viewpoint of shape retention after coating. Furthermore, from the viewpoint of preventing the resin composition from getting stuck during bonding and improving moisture resistance and adhesion, nanosilica with an average particle size of 10 to 750 nm is more preferred, and nanosilica with an average particle size of 20 to 600 nm is even more preferred. Commercially available products include, but are not limited to, hydrophobic fumed silica from CABOT (product name: CAB-O-SIL(registered trademark) TS720, average particle size: 12 nm), hydrophobic fumed silica from Nippon Aerosil (product name: R805, average particle size: 20 nm), and amorphous silica from Nippon Shokubai (product name: Seahoster KE-P10, average particle size: 100 nm). Here, the average particle size of nanosilica particles is measured using a dynamic light scattering nanotrack particle size analyzer. The quinotropizing agent may be used alone or in combination of two or more types.

[0078] If a quinostat is included, the quinostat content is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and even more preferably 0.1 to 20% by mass, based on the total mass of the photocurable resin composition.

[0079] • Light-blocking agent The photocurable resin composition according to this embodiment may contain a light-shielding agent to the extent that it does not impair the effects of this embodiment. Depending on the intended use of the cured resin composition, light-shielding properties may be required. In such cases, the photocurable resin composition according to this embodiment may contain a light-shielding agent. Long-wavelength light can penetrate light-shielding agents that block ultraviolet light. The photocurable resin composition according to this embodiment can be cured by irradiation with long-wavelength light, with little to no effect from the light-shielding agent. Examples of light-shielding agents include, but are not limited to, carbon black and titanium black. Furthermore, these light-shielding agents can also be used as photothermal conversion materials that convert long-wavelength light into heat.

[0080] Photon Upconversion Materials The photocurable resin composition according to this embodiment may contain a photon upconversion (PUC) material, to the extent that it does not impair the effects of this embodiment. Photon upconversion materials generate high-energy states through multiphoton excitation, triplet-triplet annihilation, etc., by absorbing specific light, and emit light with a shorter wavelength than the incident light during the relaxation process. By incorporating this photon upconversion material into a resin composition, the photon upconversion material performs wavelength conversion of long-wavelength light within the resin composition. For example, in one embodiment, by using a combination of (B) exhausted emission (OSL) material and photon upconversion material, energy transfer becomes possible within the resin composition from the (B) exhausted emission (OSL) material to the photon upconversion material, or from the photon upconversion material to the (B) exhausted emission (OSL) material. Through such stepwise energy transfer, the emission wavelength of the (B) exhausted emission (OSL) material can be adjusted so that it ultimately includes wavelengths less than 500 nm from the desired incident light, thereby enabling photocuring of the resin composition using the desired incident light. The wavelength range of the excitation light that causes such a photon upconversion material to emit upconversion light is preferably a wavelength greater than 500 nm, for example, a wavelength within the range of greater than 500 nm and less than or equal to 2000 nm.

[0081] Photon upconversion (PUC) is a technology that converts low-energy (long-wavelength) light into high-energy (short-wavelength) light. Mechanisms of photon upconversion include triplet-triplet annihilation (TTA), multiphoton excitation of rare-earth element-containing materials, and two-photon absorption. In this embodiment, a photon upconversion material based on any of these mechanisms can be used, but it is preferable that the photon upconversion material is a triplet-triplet annihilation type photon upconversion material, a multiphoton excitation type photon upconversion material, or a combination thereof.

[0082] Triplet-triplet annihilation type photon upconversion material In one embodiment, the photon upconversion material is a triplet-triplet annihilation type photon upconversion material. In a triplet-triplet annihilation type photon upconversion material, a combination of a donor and an acceptor is used. Examples of triplet-triplet annihilation type photon upconversion materials that can be used are those described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030.

[0083] <Acceptor> The acceptor (acceptor compound) is not particularly limited, as long as it is a compound (luminescent material) that, after receiving triplet energy transfer from the donor, becomes an excited singlet state and can produce photon upconversion luminescence. Examples of acceptors include, but are not limited to, compounds containing naphthalene, anthracene, tetracene, pyrene, perylene, biphenyl, terphenyl, perylenediimide, naphthalenediimide, and BODIPY (boron dipyromethene; 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) structures. Specific examples of acceptors include, but are not limited to, 9,10-diphenylanthracene (DPA), tetra-tert-butylperylene, anthracene (An), 2,5-diphenyloxazole (PPO), rubrene, 2-chloro-bis-phenylethynylanthracene (2CBPEA), 9,10-bis(phenylethynyl)anthracene (BPEA), 9,10-bis(phenylethynyl)naphthacene (BPEN), perylene, coumarin 343 (C343), 9,10-dimethylanthracene (DMA), pyrene, tert-butylpyrene, and boron dipyromethene (BODIPY) derivatives BD-1 and BD-2 having an iodophenyl group, as well as halogenated derivatives of these compounds. Other specific examples of acceptors include, for example, those described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030.

[0084] <Donor> The donor (donor compound) is not particularly limited as long as it absorbs incident light, becomes an excited triplet state through intersystem crossing from an excited singlet state, and causes triplet-triplet energy transfer to the acceptor. Examples of donors include, but are not limited to, metal atoms such as Pt, Pd, Zn, Ru, Re, Ir, Os, Cu, Ni, Co, Cd, Au, Ag, Sn, Sb, Pb, P, As, and compounds containing organic moieties such as porphyrin structures, phthalocyanine structures, fullerene structures, and 2-phenylpyridinate structures. Specific examples of donors include palladium octabtoxicphthalocyanine (PdOBuPc), platinum tetraphenyltetranaphthoporphyrin (PtTPTNP), palladium(II)-meso-tetraphenyl-tetrabenzoporphyrin (PdTPTBP), and [Ru(dmb)3] 2+ (dmb is 4,4'-dimethyl-2,2'-bipyridine), palladium(II) tertraanthraporphyrin (PdTAP), platinum(II) tetraphenyltetrabenzoporphyrin (PtTPBP), palladium mesotetraphenyltetrabenzoporphyrin (PdPh4TBP), palladium octaethylporphyrin (PdOEP), 11,15,18,22,25 octa-toxyphthalocyanine (PdPc(OBu)8), octaethylporphyrin (OEP), platinum octaethylporphyrin Phosphorus (PtOEP), zinc(II) octaethylporphyrin (ZnOEP), zinc(II) meso-tetraphenylporphyrin (ZnTPP), palladium(II) tetraphenyltetrabenzoporphyrin (PdTPBP), palladium(II) meso-tetraphenyl-octamethoxydotetranaphtholporphyrin (PdPh4OMe8TNP), 2-methoxythioxanthone (2MeOTX), and Ir(ppy)3 (ppy=2-phenylpyridine) are examples of, but are not limited to, these. Other specific examples of donors include, for example, those described in Japanese Patent Publication No. 2021-080335 and Japanese Patent Publication No. 2020-056030.

[0085] The wavelengths of incident and emitted light can be controlled by appropriately selecting the combination and molar ratio of donors and acceptors. The combination of donors and acceptors may be one set or two or more sets. The molar ratio of donors to acceptors can be, for example, donor:acceptor = 1:1 to 1:100,000.

[0086] • Multiphoton excitation type photon upconversion materials In one embodiment, the photon upconversion material is a multiphoton-excited type photon upconversion material. A multiphoton-excited type photon upconversion material is a material that emits upconversion light upon multiphoton excitation.

[0087] In multiphoton-excited photon upconversion materials, a rare earth element is doped into an optically inert matrix material, thereby exhibiting upconversion emission characteristics. By appropriately selecting the type and amount (doping amount) of rare earth element contained in the multiphoton-excited photon upconversion material, upconversion emission at any desired wavelength can be obtained.

[0088] While there are no particular limitations on the rare earth elements that can perform upconversion luminescence, generally speaking, rare earth elements that form trivalent ions can be mentioned. In particular, it is preferable to use a combination of at least two rare earth elements selected from the group consisting of erbium (Er), holomium (Ho), praseodymium (Pr), thulium (Tm), neodymium (Nd), gadolinium (Gd), europium (Eu), ytterbium (Yb), samarium (Sm), and cerium (Ce).

[0089] The base material (matrix) is a material that supports rare earth elements, and is not particularly limited as long as it supports the rare earth elements in a state capable of upconversion luminescence. It may be an organic material that reacts with the rare earth elements to form complexes, dendrimers, etc., or it may be an inorganic material. An inorganic material is preferred because it is easy to incorporate the rare earth elements in a state capable of luminescence.

[0090] From the viewpoint of luminescence efficiency, materials that are transparent to excitation light are preferred as the inorganic base material for such materials. Specifically, halides such as fluorides and chlorides, oxides, sulfides, and oxysulfides are particularly suitable. Examples of such halides include, but are not limited to, barium chloride (BaCl2), lead chloride (PbCl2), lead fluoride (PbF2), cadmium fluoride (CdF2), lanthanum fluoride (LaF3), and yttrium fluoride (YF3). Examples of oxides include, but are not limited to, yttrium oxide (Y2O3), cerium oxide (CeO2), aluminum oxide (Al2O3), silicon dioxide (SiO2), and tantalum oxide (Ta2O5). A coating material may be formed around the multiphoton-excited type photon upconversion material using a halide as the base material. The oxides listed above can be used as this coating material.

[0091] Additionally, a core-shell type upconversion material consisting of a core (NaYREF4) and a shell (NaYF4) (RE = rare earth element) can also be used.

[0092] Multiphoton-excited photon upconversion materials can be manufactured by known methods, such as gas evaporation including high-frequency plasma methods, sputtering, glass crystallization, chemical deposition, reverse micelle methods, sol-gel methods and similar methods, precipitation methods including hydrothermal synthesis and coprecipitation, or spray methods. For example, a method for manufacturing multiphoton-excited photon upconversion materials can be found in Japanese Patent Application Publication No. 2006-117864. Commercially available multiphoton-excited photon upconversion materials may also be used.

[0093] • Other additives The resin composition of this embodiment may, if desired, further contain other additives, such as photosensitizers, conductive fillers, radical polymerization inhibitors, anionic polymerization inhibitors, cationic polymerization inhibitors, coupling agents, ion trapping agents, leveling agents, antioxidants, defoaming agents, viscosity modifiers, flame retardants, colorants, plasticizers, solvents, etc., to the extent that the spirit of this embodiment is not impaired. The type and amount of each additive are as per conventional methods.

[0094] The viscosity of the resin composition according to this embodiment is preferably 0.1 to 100 Pa·s. The viscosity can be adjusted as appropriate depending on the application and location of the resin composition. The resin composition according to this embodiment is excellent for application to areas with complex shapes where UV light irradiation is difficult, and for application to narrow areas. In this specification, unless otherwise specified, viscosity is expressed as a value measured in accordance with the Japanese Industrial Standard JIS K6833. Specifically, it can be determined by measuring with an E-type viscometer at a rotation speed of 10 rpm. There are no particular restrictions on the equipment, rotor, or measurement range used.

[0095] The resin composition of this embodiment can be a one-component resin composition contained in a single container, or a two-component (or multi-component) resin composition contained in two or more containers, depending on its intended use. In the case of a two-component (or multi-component) resin composition, the two components (or multi-component) are mixed at the time of use to form a photocurable resin composition in the intended use form. When a two-component (or multi-component) resin composition is used, components (A) and (B) or components (A) to (C), and other optional components as needed can be selected in the same way as in the one-component type. Furthermore, when a two-component (or multi-component) resin composition is used, components (A) and (B) or components (A) to (C), and other optional components as needed can be separated into two or multiple components in any way without particular restriction. However, in the case of a two-component (or multi-component) resin composition, (C) selected from the group consisting of (B) an exhausted luminescence (OSL) material, a maleimide compound described below, and (C) a photopolymerization initiator. 0 It is preferable that the initiator and the other are separated into different liquids. In that case, (A) described below 0 ) One or more polymerizable compounds and other optional components as needed, (B) liquid containing exhausted luminescence (OSL) material, and (C 0 The initiator may be present in either one of the solutions, or in both.

[0096] Another aspect of the present invention is that one of the liquids in a two-component resin composition is (A 0 ) Polymerizable compounds, and (B) Exhausted Luminescence (OSL) Materials (C 0 ) is a main component composition that substantially does not contain an initiator. In this embodiment, (A 0 ) The polymerizable compounds are as defined in (A) above, except for maleimide compounds. In this embodiment, (C 0The initiator is selected from the group consisting of maleimide compounds and (C) photopolymerization initiators. Here, the maleimide compounds and (C) photopolymerization initiators are as defined above. The main composition may contain other optional components as needed. The other optional components are as defined above.

[0097] Another aspect of the present invention is, (1) The main component composition described above, and (2)(C 0 ) Initiator composition containing an initiator This is a photocurable resin composition kit containing (C 0 The initiator is selected from the group consisting of maleimide compounds and (C) photopolymerization initiators. Here, the maleimide compounds and (C) photopolymerization initiators are as defined above. In one embodiment of this aspect, (2) the initiator composition is (A 0 ) may further contain polymerizable compounds. In this embodiment, (A 0 ) The polymerizable compounds are as defined in (A) above, except for maleimide compounds. The main composition and the initiator composition are each (A 0 The inclusion of polymerizable compounds facilitates uniform mixing of the main composition and the initiator composition. The initiator composition may contain other optional components as needed. Other optional components are as defined above.

[0098] It is preferable that the (B) exhausted luminescence (OSL) material contained in the photocurable resin composition has accumulated excitation energy before the photocurable resin composition is used for curing by irradiation with long wavelength light (e.g., 500 nm or more). A method for accumulating excitation energy in the (B) exhausted luminescence (OSL) material is, for example, by irradiating the (B) exhausted luminescence (OSL) material with radiation. The radiation is preferably near-ultraviolet, far-ultraviolet, X-ray, gamma ray, or any combination thereof. Near-ultraviolet has a wavelength of 200 nm to 380 nm. Far-ultraviolet has a wavelength of 10 nm to 200 nm. X-ray has a wavelength of 0.01 nm to 10 nm. Gamma ray has a wavelength of 0.000001 nm to 0.01 nm. Depending on the type and amount of exhausted luminescence (OSL) material, the type of radiation, the cumulative irradiation dose, and the irradiation intensity can be adjusted as appropriate. In one embodiment, the radiation used is radiation with a shorter wavelength than the emission wavelength of the exhausted luminescence (OSL) material. In one embodiment, the radiation used is radiation with an energy higher than the band gap of the inorganic exhausted luminescence (OSL) material. In one embodiment, the radiation is X-rays. In one embodiment, the radiation is far ultraviolet light. The radiation irradiation time may vary depending on the type and amount of exhausted luminescence (OSL) material and the type of radiation, but may be, for example, 1 second to 24 hours. The number of radiation irradiations may be one, two or more. In one embodiment, a method for accumulating excitation energy in (B) exhausted luminescence (OSL) material may be a method of irradiating the (B) exhausted luminescence (OSL) material alone with radiation. In one embodiment, (B) a method for accumulating excitation energy in an exhausted luminescence (OSL) material is (A 0 (B) A method of irradiating a composition comprising a polymerizable compound and (C) an exhausted luminescence (OSL) material with radiation. However, this composition is selected from the group consisting of a maleimide compound and (C) a photopolymerization initiator. 0 ) Does not contain an initiator. (A 0The polymerizable compound is as defined in (A) above, except for maleimide compounds. This allows for efficient storage of excitation energy in the exhausted luminescence (OSL) material. This composition may contain other optional components as needed. Other optional components are as defined above. This composition may be the main component composition of the above embodiment. In one embodiment, a method for accumulating excitation energy in (B) an exhausted luminescence (OSL) material is a photocurable resin composition comprising (A) a polymerizable compound and (B) an exhausted luminescence (OSL) material, satisfying at least one of the following features (a) and (b): (a)(A) The polymerizable compound includes a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. This method involves irradiating a photocurable resin composition with radiation. By directly irradiating a one-component resin composition with radiation, excitation energy can also be accumulated in the (B) exhausted luminescence (OSL) material. This photocurable resin composition may contain other optional components as needed. The other optional components are as defined above.

[0099] The method for producing the photocurable resin composition according to this embodiment is not particularly limited, but it is preferable to include a step of (B) accumulating excitation energy in an exhausted luminescence (OSL) material. That is, another embodiment of the present invention is a method for producing the photocurable resin composition, (B) A method for producing a photocurable resin composition, comprising a step of accumulating excitation energy in an OSL (Optical Saturation Luminescence) material. In one embodiment, the step of accumulating excitation energy in the (B) exhausted luminescence (OSL) material may be irradiating the (B) exhausted luminescence (OSL) material alone with radiation. In one embodiment, the step of accumulating excitation energy in the (B) exhausted luminescence (OSL) material is (A 0 (B) Irradiating a composition comprising a polymerizable compound and an exhausted luminescence (OSL) material with radiation. However, this composition is (C 0(A) Does not contain an initiator selected from the group consisting of maleimide compounds and (C) photopolymerization initiators. 0 The polymerizable compound is as defined in (A) above, except for maleimide compounds. This composition may contain other optional components as needed. Other optional components are as defined above. This composition may be the main component composition of the embodiment described above. In one embodiment, the step of accumulating excitation energy in the (B) exhausted luminescence (OSL) material is a photocurable resin composition comprising (A) a polymerizable compound and (B) exhausted luminescence (OSL) material, which satisfies at least one of the following features (a) and (b): (a)(A) The polymerizable compound includes a maleimide compound; (b) The photocurable resin composition further comprises (C) a photopolymerization initiator. This includes irradiating a photocurable resin composition with radiation. This photocurable resin composition may optionally contain other optional components, as defined above.

[0100] In the case of a one-component resin composition, (B) as a step of accumulating excitation energy in the exhausted luminescence (OSL) material, (B) after irradiating the exhausted luminescence (OSL) material alone with radiation, or (A 0 A photocurable resin composition according to this embodiment can be obtained by irradiating a composition containing (A) a polymerizable compound and (B) an exhausted luminescence (OSL) material with radiation, and then introducing (A) a polymerizable compound, (B) an exhausted luminescence (OSL) material, (C) a photopolymerization initiator if necessary, and other optional components if necessary, simultaneously or separately into a suitable mixer, stirring and mixing to obtain a homogeneous composition. Alternatively, in the case of a one-component resin composition, the photocurable resin composition according to this embodiment can be obtained by simultaneously or separately introducing (A) a polymerizable compound, (B) an exhausted luminescence (OSL) material, (C) a photopolymerization initiator if necessary, and other optional components if necessary into a suitable mixer, stirring and mixing them to obtain a homogeneous composition, and then subjecting the composition to a step in which excitation energy is accumulated in (B) the exhausted luminescence (OSL) material. In the case of a two-component resin composition, (B) after the step of accumulating excitation energy in the exhausted luminescence (OSL) material, for example, (A 0 (B) A main composition comprising a polymerizable compound, (C) an exhausted luminescence (OSL) material and other optional components as needed, and (C 0 ) Initiator, as needed (A 0 The photocurable resin composition according to this embodiment can be obtained by mixing an initiator composition containing a polymerizable compound and other optional components as needed using a suitable mixer. Alternatively, in the case of a two-component resin composition, (A 0 (B) A main composition comprising a polymerizable compound, (C) an exhausted luminescence (OSL) material and other optional components as needed, and (C 0 ) Initiator, as needed (A 0 A photocurable resin composition according to this embodiment can be obtained by mixing an initiator composition containing a polymerizable compound and other optional components as needed using a suitable mixer to obtain a homogeneous composition, and then subjecting that composition to a step of accumulating excitation energy in an exhausted luminescence (OSL) material. The mixer used for mixing is not particularly limited, but a Leikai mixer, Henschel mixer, three-roll mill, ball mill, planetary mixer, and bead mill, etc., equipped with a stirring device and a heating device, can be used. These devices may also be used in appropriate combinations.

[0101] The photocurable resin composition obtained in this way is cured by irradiation with long-wavelength light (for example, 500 nm or more), and can be cured by light irradiation alone. Conventional UV-curable adhesives typically use high-energy, short-wavelength light (e.g., 365nm UV light) for photocuring. Therefore, if the adhesive contains fillers, short-wavelength light irradiation results in a short penetration distance into the UV-curable adhesive, and curing does not proceed in areas where light cannot reach due to shielding materials. Regarding the latter in particular, if we examine the relationship between the wavelength of the irradiated light and the penetration distance of the light into the silicon substrate, for example, using a silicon substrate as the shielding material, ultraviolet light below 380nm penetrates the silicon substrate at a penetration distance of several to tens of nanometers, while visible light between 380 and 780nm penetrates at hundreds of nanometers to several microns, and infrared light above 780nm penetrates at a depth of tens of microns to millimeters (e.g., Optical Properties of Silicon, [online], PVEducation,<https: / / www.pveducation.org / pvcdrom / materials / optical-properties-of-silicon> (See reference). Although the penetration distance of light into a resin composition during ultraviolet light irradiation is deeper than that of a silicon substrate, increasing the irradiation wavelength is a useful method for improving the degree of curing of the resin composition.

[0102] The photocurable resin composition according to this embodiment can be used, for example, as an adhesive, encapsulant, or coating agent, or as a raw material, for fixing, joining, or protecting semiconductor devices or electronic components, or the components that constitute them. In one embodiment, the photocurable resin composition according to this embodiment can be cured by irradiation with light of a wavelength of 500 nm or more. In one embodiment, the photocurable resin composition according to this embodiment can be used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

[0103] [Adhesion method] Another aspect of the present invention is a method for bonding at least two parts with a photocurable resin composition, wherein the bonding method is The steps include applying the photocurable resin composition according to the above embodiment to at least one of the at least two components, and The process includes irradiating at least one of the at least two components, the photocurable resin composition, or both thereof with light having a wavelength of 500 nm or more.

[0104] As a first step, the photocurable resin composition according to the above embodiment is applied to at least one of at least two parts. The component is preferably a component that constitutes a semiconductor device or electronic component, such as a semiconductor element or substrate, but is not limited to these. The material of the component may be any of the following: engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel). The method of applying the resin composition is not particularly limited, and for example, it can be applied to a desired part of a substrate or other component by known printing, dispensing, or coating methods. Examples of printing methods include, but are not limited to, inkjet printing, screen printing, lithographic printing, cardboard printing, metal printing, offset printing, gravure printing, and flexographic printing. Examples of dispensing methods include, but are not limited to, methods using jet dispensers and air dispensers. Examples of coating methods include, but are not limited to, dip coating, spray coating, bar coater coating, gravure coating, reverse gravure coating, and spin coater coating.

[0105] Next, one part is attached to the part coated with the photocurable resin composition via the photocurable resin composition, or the part coated with the photocurable resin composition is attached to the other part via the photocurable resin composition. Any known method of attachment may be used. If necessary, the parts can be pressed together under load after attachment.

[0106] Next, at least one of the at least two components, the photocurable resin composition, or both of them are irradiated with light of a wavelength of 500 nm or more, for example, light in the range of 500 nm to 2000 nm, as a stimulating light. This causes the exhausted luminescence (OSL) material inside the resin composition to generate OSL with a wavelength of less than 500 nm, preferably OSL with a wavelength of 450 nm or less, more preferably OSL with a wavelength of 430 nm or less, and even more preferably OSL with a wavelength of 400 nm or less, thereby activating the photopolymerization initiator, curing the polymerizable compound, and bonding the at least two components. Furthermore, when using the exhausted luminescence (OSL) material in combination with a photon upconversion (PUC) material that can convert long-wavelength light to short-wavelength light, the photon upconversion (PUC) light obtained from the photon upconversion (PUC) material by long-wavelength light irradiation can be used as a stimulating light to generate OSL from the exhausted luminescence (OSL) material. The wavelength of the irradiated light may be, for example, 532 nm, 650 nm, 940 nm, 980 nm, 1064 nm, or 1550 nm, but is not limited to these wavelengths. The light source may be an LED, laser, LD module, or other coherent light source. The integrated irradiation dose of the irradiated light is 1 mJ / cm². 2 ~2000 J / cm 2 This is possible. The irradiation intensity is 1 mW / cm². 2 ~1000W / cm 2 This is possible. Depending on the desired degree of curing, the cumulative irradiation amount and irradiation intensity of the irradiation light can be adjusted as appropriate. In this embodiment, either spot irradiation, which irradiates a local area with light, or area irradiation, which irradiates a wide area with light, can be performed. Since the photocurable resin composition used in this embodiment can be cured even in the shaded areas of the part, in the bonding method of this embodiment, not only can the photocurable resin composition be irradiated with light directly, but light can also be irradiated through the part. Heat may be applied during light irradiation as needed.

[0107] [Sealing method] Furthermore, another aspect of the present invention is a method for sealing gaps between or within parts with a curable resin composition, the sealing method being A step of applying or injecting the photocurable resin composition according to the above embodiment into the gaps between or within the parts, and The process includes irradiating the photocurable resin composition with light having a wavelength of 500 nm or more. The components and light irradiation are the same as those in the bonding method described above. As for the application or injection method, in addition to the application method in the bonding method described above, a potting method is also included, but is not limited to these. The photocurable resin composition used in this embodiment allows for a high curing depth, and therefore, in the sealing method of this embodiment, the resin composition located deep within gaps where ultraviolet light is difficult to reach, as well as the shaded areas of the parts, can be cured, enabling suitable sealing.

[0108] [Coating Method] Furthermore, another aspect of the present invention is a method for coating the surface of an object with a photocurable composition, the method being: A step of applying the photocurable resin composition according to the above embodiment to the object, and The process includes irradiating the photocurable resin composition with light having a wavelength of 500 nm or more. The object may be a semiconductor device or electronic component, or a component comprising them. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. Examples of components comprising semiconductor devices or electronic components include, but are not limited to, semiconductor elements and substrates. The material of the component may be any of the following: engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, or metals (e.g., copper, nickel). The application method is the same as that used in the bonding method described above. The light irradiation method is the same as that used in the bonding method described above.

[0109] [Adhesives, sealants, or coatings] Another embodiment of the present invention, an adhesive, sealant, or coating agent, comprises a photocurable resin composition of the said embodiment. This adhesive, sealant, or coating agent enables good fixation, bonding, or protection of engineering plastics (e.g., LCP (liquid crystal polymer), polyamide, polycarbonate, etc.), ceramics, and metals (e.g., copper, nickel, etc.), and can be used to fix, bond, or protect semiconductor devices or electronic components or the components that constitute them. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits. The adhesive, sealant, or coating agent of this embodiment can be cured by irradiation with long-wavelength light (e.g., 500 nm or more), thus offering high productivity and suitability for use, for example, in the manufacturing of semiconductor devices and electronic components.

[0110] [Cured products of resin compositions, adhesives, sealants, or coatings] Another embodiment of the present invention is a cured product obtained by curing the photocurable resin composition or adhesive, sealant, or coating agent of the above embodiment.

[0111] [Semiconductor equipment, electronic components] Another embodiment of the present invention provides a semiconductor device or electronic component that includes the cured product of the above embodiment, and therefore these semiconductor devices or electronic components have high reliability. Here, "semiconductor device" refers to all devices that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc. Examples of semiconductor devices or electronic components include, but are not limited to, HDDs, semiconductor elements, sensor modules such as image sensor modules, other semiconductor modules, and integrated circuits.

[0112] [Curing method, manufacturing method of cured product] Another aspect of the present invention is a method for producing a cured product, comprising irradiating a photocurable resin composition of the above-described aspect, or an adhesive, sealant, or coating agent of the above-described aspect, with light having a wavelength of 500 nm or more. Yet another aspect of the present invention is a method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition of the above-described aspect with light having a wavelength of 500 nm or more. Yet another aspect of the present invention is the use of the photocurable resin composition of the above-described aspect for curing by irradiation with light having a wavelength of 500 nm or more. By irradiating with light having a wavelength of 500 nm or more as a stimulating light, for example, light in the range of 500 nm to 2000 nm, the photocurable resin composition can generate exhausted luminescence (OSL) material with a wavelength of less than 500 nm, preferably OSL with a wavelength of 450 nm or less, more preferably OSL with a wavelength of 430 nm or less, thereby activating the initiator and curing the polymerizable compound. The details of the irradiation with light having a wavelength of 500 nm or more in these methods are the same as those in the bonding method, sealing method, and coating method described above. In this embodiment, either spot irradiation, which irradiates a local area with light, or area irradiation, which irradiates a wide area with light, can be performed. [Examples]

[0113] The present invention will be described in more detail below with reference to examples, comparative examples, and reference examples, but the present invention is not limited to these examples. In the following examples, parts and % refer to parts by mass and mass%, respectively, unless otherwise specified.

[0114] [Manufacturing of one-component photocurable resin composition] One-component photocurable resin compositions for Examples 1-21, Comparative Examples 1-5, and Reference Examples 1-5 were prepared by mixing predetermined amounts of each component according to the formulations shown in Table 1. In Table 1, the amounts of each component are expressed in mass%. The total of (A) polymerizable compound, (C) photopolymerization initiator, (D) filler, and (E) thixotrope was set to 100% by mass, to which (B) exhausted luminescence (OSL) material was added in the mass% shown in Table 1. For Example 21 and Comparative Example 5, the photon upconversion (PUC) material was added in the mass% shown in Table 1 to the total of 100% by mass of (A) polymerizable compound, (C) photopolymerization initiator, (D) filler, and (E) thixotrope. In Examples 1 to 21, before mixing each component, the (B) exhausted luminescence (OSL) material was irradiated with X-rays to accumulate excitation energy in the (B) exhausted luminescence (OSL) material. The X-ray irradiation was performed using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA), with one set consisting of 5 minutes of X-ray irradiation followed by stirring of the exhausted luminescence (OSL) material, and this was repeated five times. On the other hand, in Reference Examples 1 to 5, the (B) exhausted luminescence (OSL) material was not irradiated with X-rays.

[0115] [Manufacturing of two-component photocurable resin compositions] By mixing predetermined amounts of each component according to the formulation shown in Table 2, (A 0 (B) A main composition comprising a polymerizable compound, (C) an exhausted luminescence (OSL) material and other optional components as needed, and (C 0 ) Initiator, as needed (A 0 An initiator composition containing a polymerizable compound and other optional components as needed was prepared. Next, the main component composition was irradiated with X-rays to accumulate excitation energy in the (B) exhausted luminescence (OSL) material. The X-ray irradiation was performed using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA), with each set consisting of 5 minutes of X-ray irradiation followed by stirring of the main component composition, and this was repeated five times. Subsequently, the two-component photocurable resin compositions of Examples 22 to 28 were prepared by mixing the main component composition and the initiator composition in a 1:1 mass ratio. In Table 2, the amount of each component is expressed in mass%.

[0116] The components used in the examples, comparative examples, and reference examples are as follows: ·(A) Polymerizable compound (A-1): Dimethylol-tricyclodecanediaacrylate (Product name: Light Acrylate DCP-A, manufactured by Kyoeisha Chemical Co., Ltd.) (A-2): Oxetane resin (Product name: OXT-221, manufactured by Toagosei Co., Ltd.) (A-3): Water-added BisA type epoxy resin (Product name: YX8000, manufactured by Mitsubishi Chemical Corporation) (A-4): Bismaleimide resin (Product name: BMI-689, Yamato Chemical Industries Co., Ltd.)

[0117] (B) Exhausted Luminescence (OSL) Materials (B-1): (La0.99Ce0.005Dy0.005)PO4 (Synthesis method shown below) Cerium nitrate and dysprosium nitrate were weighed to a concentration of 0.5 mol% relative to lanthanum nitrate. Next, these metal nitrates were weighed to phosphoric acid in a molar ratio of 1:1. These raw materials were dissolved in pure water, placed in a 100 ml Teflon® container, and heat-treated at 140°C for 6 hours. The resulting precipitate was filtered, washed, and dried, then placed in an aluminium and calcined at 1200°C for 6 hours in an air atmosphere. The X-ray diffraction pattern of the obtained substance was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. Furthermore, the obtained compound was irradiated with X-rays for 5 minutes, allowed to stand in the dark at 60°C for 10 minutes, and then the OSL at 320 nm was observed by irradiation with 532 nm stimulation light. (B-2): (Y0.99Ce0.005Nd0.005)PO4 (Synthesis method shown below) Cerium nitrate and neodymium nitrate were weighed to a concentration of 0.5 mol% relative to yttrium nitrate. Next, these metal nitrates were weighed to phosphoric acid in a molar ratio of 1:1. These raw materials were dissolved in pure water, placed in a 100 ml Teflon® container, and heat-treated at 140°C for 6 hours. The resulting precipitate was filtered, washed, and dried, then placed in an aluminium and calcined at 1200°C for 6 hours in an air atmosphere. The X-ray diffraction pattern of the obtained substance was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. Furthermore, the obtained compound was irradiated with X-rays for 5 minutes, allowed to stand in the dark at 60°C for 10 minutes, and then the OSL at 320 nm was observed by irradiation with 532 nm stimulation light. (B-3): (La0.993Ce0.005Dy0.002)PO4 (Synthesis method shown below) Cerium nitrate was weighed to a concentration of 0.5 mol% and dysprosium nitrate to 0.2 mol relative to lanthanum nitrate. Next, these metal nitrates were weighed to phosphoric acid in a molar ratio of 1:1. These raw materials were dissolved in pure water, placed in a 100 ml Teflon® container, and heat-treated at 140°C for 6 hours. The resulting precipitate was filtered, washed, and dried, then placed in an aluminium and calcined at 1200°C for 6 hours in an air atmosphere. The X-ray diffraction pattern of the obtained substance was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. Furthermore, the obtained compound was irradiated with X-rays for 5 minutes, allowed to stand in the dark at 60°C for 10 minutes, and then the OSL at 320 nm was observed by irradiation with 532 nm stimulation light. (B-4): (Y0.99Ce0.005Dy0.005)PO4 (Synthesis method shown below) Cerium nitrate and dysprosium nitrate were weighed to a concentration of 0.5 mol% relative to yttrium nitrate. Next, these metal nitrates were weighed to phosphoric acid in a molar ratio of 1:1. These raw materials were dissolved in pure water, placed in a 100 ml Teflon® container, and heat-treated at 140°C for 6 hours. The resulting precipitate was filtered, washed, and dried, then placed in an aluminium and calcined at 1200°C for 6 hours in an air atmosphere. The X-ray diffraction pattern of the obtained substance was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. Furthermore, the obtained compound was irradiated with X-rays for 5 minutes, allowed to stand in the dark at 60°C for 10 minutes, and then the OSL at 320 nm was observed by irradiation with 532 nm stimulation light. (B-5): (La0.99966Ce0.00017Dy0.00017)PO4 (Synthesis method is shown below) 0.006 mol of lanthanum nitrate, and 0.000001 mol each of cerium nitrate and dysprosium nitrate were weighed out. These raw materials were dissolved in pure water, and 0.071 mol% of citric acid was added relative to the total amount of lanthanum, cerium, and dysprosium contained in these raw materials and mixed. Then, an aqueous phosphoric acid solution was added dropwise to the lanthanum nitrate in a 1:1 molar ratio. The resulting precipitate was collected using a centrifuge, washed, and dried, and then calcined in a quartz watch glass at 1000°C for 3 hours in an atmospheric atmosphere. The X-ray diffraction pattern of the obtained substance was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. In addition, the obtained compound was irradiated with X-rays for 5 minutes, allowed to stand in the dark at 60°C for 10 minutes, and then the OSL at 320 nm was observed by irradiation with 532 nm stimulation light.

[0118] (C) Photopolymerization initiator (C-1): 2-Dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-ylphenyl)-butan-1-one (Product name: Omnirad 379EG, manufactured by IGM Resins BV, photoradical polymerization initiator) (C-2): 1-Hydroxycyclohexylphenyl ketone (product name: Omnirad 184, manufactured by IGM Resins BV, photoradical polymerization initiator) (C-3): Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Omnirad 819, manufactured by IGM Resins BV, photoradical polymerization initiator) (C-4): Sulfonium, tris[4-[(4-acetylphenyl)thio]phenyl]-, tetrakis(2,3,4,5,6-pentafluorophenyl) borate (product name: Omnirad 290, manufactured by IGM Resins BV, photoacid generator)

[0119] (D) Filler (D-1): High-purity synthetic spherical silica (Product name: SE-2300, manufactured by Admatex Co., Ltd., volume average particle size: 0.6 μm) (E) Thickening agent (E-1): Hydrophobic fumed silica (Product name: CAB-O-SIL(registered trademark) TS720, manufactured by CABOT, average particle size: 12 nm) (F) Light-blocking agent (F-1): Carbon Black (Product Name: Special Black 4, manufactured by Orion Engineered Carbons Co., Ltd.) • (G) Photon Upconversion (PUC) Materials (G-1)Ce0.977Ho0.003Yb0.02O2 (Synthesis method is shown below) Cerium oxide, holmium oxide, and terbium oxide were weighed and mixed and ground so that the molar ratio of cerium, holmium, and ytterbium elements was 0.997:0.003:0.02. Next, this mixture was placed in an alumina and calcined at 1400°C for 6 hours in an air atmosphere. The X-ray diffraction pattern of the obtained material was obtained using an X-ray diffractometer (Rigaku Ultima4, X-ray source CuKα, tube voltage 40kV, tube voltage 40mA) to confirm that it was the target compound. Furthermore, using a fluorescence spectrophotometer (Shimadzu RF-6000), the obtained material was irradiated with near-infrared light at 900nm, and it was confirmed that strong upconversion light was generated around 540nm.

[0120] In the examples, comparative examples, and reference examples, the curing of the resin composition was determined by measuring it as follows.

[0121] [Measurement of response rate] In this specification, the curing of resin compositions was determined by the change in reaction rate using the total internal reflection (ATR) method. The ATR spectrum was measured using an infrared spectrophotometer (Perkin Elmer Spectrum3) equipped with an ATR stage. A small amount of the resin composition for each example, comparative example, and reference example was dropped onto a glass plate (76 mm x 26 mm x 1.2-1.5 mm thick), and the glass plate was placed on top of it and sandwiched between the samples to create the measurement samples. Stimulation light irradiation was performed using visible light at a wavelength of 532 nm, visible light at a wavelength of 650 nm, and near-infrared light at a wavelength of 940 nm. For visible light irradiation, an LED light source (4-color LED light, Alonefire) was used, with the light source positioned 4 cm above the top surface of the measurement sample, and the wavelength was 532 nm or 650 nm, with an irradiation intensity of 10 mW / cm². 2 And the accumulated light intensity is 6000 mJ / cm 2 The sample was continuously irradiated for 10 minutes until the desired result was reached. The near-infrared light irradiation experiment was conducted using an LED light source (CL-H1-940-9-1-A, manufactured by Asahi Spectroscopic Co., Ltd.), with the sample positioned 4 cm above the light source, at a wavelength of 940 nm and an irradiation intensity of 10 mW / cm². 2 And the accumulated light intensity is 6000 mJ / cm 2 The material was continuously irradiated for 10 minutes until the desired result was reached. After light irradiation, the glass plate was removed, and the ATR spectrum of the hardened component was obtained. The reaction rate was defined as the percentage change in the C=C / C=O stretching vibration peak area ratio in the ATR spectrum when irradiated with LED light, compared to the C=C / C=O stretching vibration peak area ratio in the ATR spectrum when no stimulating light was applied. If a cured product was obtained that could be visually confirmed and the reaction rate increased, it was determined to be cured (indicated as ○). If a cured product could not be visually confirmed but the reaction rate increased, it was determined to be partially cured (indicated as △). If a cured product could not be visually confirmed and no change in the reaction rate was observed, it was determined to be uncured (indicated as ×).

[0122] [Table 1-1]

[0123] [Table 1-2]

[0124] [Table 1-3]

[0125] [Table 1-4]

[0126] [Table 2]

[0127] As can be seen from Tables 1 and 2, the photocurable resin compositions of Examples 1 to 28, which included (B) exhausted luminescence (OSL) material with accumulated excitation energy, underwent curing upon irradiation with light of a wavelength of 500 nm or higher. The (B) exhausted luminescence (OSL) material is not limited to those listed in Tables 1 and 2; similar results can be obtained by using any exhausted luminescence (OSL) material in which OSL is observed. The resin compositions of Reference Examples 1 to 5 did not cure when irradiated with light of a wavelength of 500 nm or higher because excitation energy was not accumulated in the (B) exhausted luminescence (OSL) material. However, excitation energy can be accumulated in the (B) exhausted luminescence (OSL) material by directly irradiating the one-component resin compositions of Reference Examples 1 to 5 with radiation.

Claims

1. (A) Polymerizable compounds, and (B) Optimal luminescence (OSL) materials A photocurable resin composition comprising the following features (a) and (b), which satisfies at least one of the following characteristics: (a) The polymerizable compound (A) contains a maleimide compound; (b) The photocurable resin composition comprises (C) a photopolymerization initiator. Photocurable resin composition.

2. The photocurable resin composition according to claim 1, wherein the polymerizable compound (A) is a radical polymerizable compound, a cationic polymerizable compound, an anionic polymerizable compound, or any combination thereof.

3. A photocurable resin composition according to claim 1 or 2, for use in curing by irradiation with light of a wavelength of 500 nm or more.

4. A photocurable resin composition according to any one of claims 1 to 3, used as an adhesive, encapsulant, or coating agent for semiconductor devices or electronic components.

5. A method for producing a photocurable resin composition according to any one of claims 1 to 4, (B) A method for producing a photocurable resin composition, comprising a step of accumulating excitation energy in an OSL (oscillating light emission) material.

6. An adhesive, sealant, or coating agent comprising the photocurable resin composition according to any one of claims 1 to 4.

7. A cured product obtained by curing a photocurable resin composition according to any one of claims 1 to 4, or an adhesive, sealant, or coating agent according to claim 6.

8. A semiconductor device or electronic component comprising the cured product described in claim 7.

9. A method for producing a cured product, comprising irradiating a photocurable resin composition according to any one of claims 1 to 4, or an adhesive, encapsulant, or coating agent according to claim 6, with light having a wavelength of 500 nm or more.

10. A method for curing a photocurable resin composition, comprising irradiating the photocurable resin composition according to any one of claims 1 to 4 with light having a wavelength of 500 nm or more.

11. Use of the photocurable resin composition according to any one of claims 1 to 4 for curing by irradiation with light of a wavelength of 500 nm or more.

12. A method for bonding at least two parts using a photocurable resin composition, A step of applying the photocurable resin composition according to any one of the at least two parts described above to at least one of them, and The process includes irradiating at least one of the at least two components, the photocurable resin composition, or both thereof with light having a wavelength of 500 nm or more. Adhesion method.

13. A method for sealing gaps between or within parts using a photocurable resin composition, A step of applying or injecting the photocurable resin composition according to any one of claims 1 to 4 into the gaps between or within the parts, and The photocurable resin composition is irradiated with light of a wavelength of 500 nm or more. Sealing method.

14. A method for coating the surface of an object with a photocurable resin composition, A step of applying the photocurable resin composition described in any one of claims 1 to 4 to the object, The process of irradiating the photocurable resin composition with light of a wavelength of 500 nm or more. A coating method including

15. (A ０ ) Polymerizable compounds, and (B) Optimal luminescence (OSL) materials (C ０ A main component composition that is substantially free of initiators.

16. (1) The main component composition according to claim 15, and (2) (C ０ ) Initiator composition containing an initiator A kit of photocurable resin compositions, including [the specified element].

17. The (2) initiator composition is (A ０ ) A photocurable resin composition kit according to claim 16, further comprising a polymerizable compound.

18. (A) An OSL (Optical Stimulation Luminescence) material used to cure polymerizable compounds.

19. The exhausted luminescence (OSL) material according to claim 18, which exhibits exhausted luminescence of a wavelength less than 500 nm when irradiated with light of a wavelength of 500 nm or more.

20. The exhausted luminescence (OSL) material according to claim 18 or 19, wherein the OSL material is an inorganic ceramic containing impurity elements that form luminescence centers and / or electron trapping centers, and the inorganic ceramic is an oxide or halide containing at least one metallic element selected from the group consisting of alkali metals, alkaline earth metals, earth metals, and rare earth metals.

21. The exhausted luminescence (OSL) material according to claim 20, wherein the impurity element forming the luminescence center is at least one selected from the group consisting of cerium (Ce), praseodymium (Pr), europium (Eu), thulium (Tm), bismuth (Bi), and carbon (C), and the impurity element forming the electron trapping center is at least one selected from the group consisting of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and carbon (C).

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